Jitao Lv

Dissolution and Microstructural Transformation of ZnO Nanoparticles under the Influence of Phosphate

The toxicity and fate of nanoparticles (NPs) have been reported to be highly dependent on the chemistry of the medium, and the effects of phosphate have tended to be ignored despite the wide existence of phosphate contamination in aqueous environments. In the present study the influence of phosphate on the dissolution and microstructural transformation of ZnO NPs was investigated. Phosphate at a low concentration rapidly and substantially reduced the release of Zn(2+) into aqueous solution. Synchrotron X-ray absorption spectroscopy and X-ray diffraction analysis reveal that interaction between ZnO NPs and phosphate induced the transformation of ZnO into zinc phosphate. Transmission electronic microscopy observation shows that the morphology of the particles changed from structurally uniform nanosized spherical to anomalous and porous material containing mixed amorphous and crystalline phases of ZnO and zinc phosphate in the presence of phosphate. To our knowledge, this is the first study in which the detailed process of phosphate-induced speciation and microstructural transformation of ZnO NPs has been analyzed. In view of the wide existence of phosphate contamination in water and its strong metal-complexation capability, phosphate-induced transformations may play an important role in the behaviors, fate, and toxicity of many other metal-based nanomaterials in the environment.

New insights into the sorption mechanism of cadmium on red mud

Effectiveness and mechanism of cadmium (Cd) sorption on original, acidified and ball milling nano-particle red muds were investigated using batch sorption experiments, sequential extraction analysis and X-ray absorption near edge structure (XANES) spectroscopy. The maximum sorption capacity of Cd was 0.16, 0.19, and 0.21 mol/kg for the original, acidified, and nano-particle red muds at pH 6.5, respectively. Both acidification and ball-milling treatments significantly enhanced Cd sorption and facilitated transformation of Cd into less extractable fractions. The Cd LIII-edge XANES analysis indicated the formation of inner-sphere complexes of Cd similar to XCdOH (X represents surface groups on red mud) on the red mud surfaces although outer-sphere complexes of Cd were the primary species. This work shed light on the potential application of red mud to remediate Cd-contaminated soils and illustrated the promising tool of XANES spectroscopy for speciation of multicomponent systems of environmental relevance.

Arsenate and cadmium co-adsorption and co-precipitation on goethite

Arsenate (As(V), AsO4(3-)) and cadmium (Cd) are among the toxic elements of most concern. Their sorption behaviors on goethite were studied by batch experiments (pH edges, isotherms and kinetics) and X-ray diffraction (XRD). Arsenic coordination environment was explored by X-ray absorbance fine structure (EXAFS) analysis. Sorption isotherms of both As(V) and Cd on goethite could be divided into the adsorption-dominated and precipitation-dominated parts, while their sorption showed different pH-dependency and sorption reversibility. Cadmium adsorption was enhanced in the presence of AsO4(3-), which could be explained by the decrease in the electrostatic potential due to the sorption of AsO4(3-) and the formation of a ternary Cd-As(V)-goethite complex. Based on the EXAFS study, AsO4(3-) adsorbed on goethite mainly formed bidentate-binuclear complex. The high loadings of Cd changed the As(V)-Fe distance and its coordination number. However, Cd did not affect the As(V) adsorption amount in the adsorption-dominated region. When As(V) and Cd formed co-precipitates, their sorption amounts were both increased. The formation of co-precipitates decreased the mobility of Cd but increased the mobility of As(V) because less As(V) was sorbed on goethite through surface complexation. This study will provide better understandings on As(V) and Cd transport and useful information on their remediation strategies.

Uptake, translocation and metabolism of polybrominated diphenyl ethers (PBDEs) and polychlorinated biphenyls (PCBs) in maize (Zea mays L.)

A hydroponic experiment was conducted in the present study to investigate and compare plant uptake, translocation and metabolism of polybrominated diphenyl ethers (PBDEs) of BDE-15, BDE-28 and BDE-47 and polychlorinated biphenyls (PCBs) of PCB-15, PCB-28 and PCB-47 in maize. Root concentrations of BDE-15, BDE-28 and BDE-47 were consistently higher than PCB-15, PCB-28 and PCB-47, respectively. A significantly positive correlation was found between logRCF (root concentration factor) and logKow of these PBDEs and PCBs, suggesting a control role of their partitioning in plant uptake. The translocation factors (TFs, Cstem/Croot) of PBDEs were generally lower than those of PCBs of the same halogen-substitutions, demonstrating easier transport of PCBs than PBDEs. Metabolites mono-, di- and tri-BDEs and PCBs were detected, suggesting the existence of in vivo metabolism of PBDEs and PCBs in maize. Dehalogenation and rearrangement of halogen atoms were identified, and some similarities but also significant differences existed between the PBDEs and PCBs. PBDEs in maize were, in general, more susceptible to metabolism compared with PCBs of the same halogen-substitutions. This is the first comparative report on the uptake, translocation and metabolism of PBDEs and PCBs in plants.

Accumulation, speciation and uptake pathway of ZnO nanoparticles in maize

Engineered nanomaterials such as ZnO nanoparticles (NPs) will inevitably enter the environment because of the large quantities produced and their widespread application. Plants comprise a fundamental living component of terrestrial ecosystems; thus, understanding the interaction between ENMs and plants is important. In the present study we conducted an integrated study by employing a combination of microscopic and spectroscopic techniques to comparatively investigate the uptake of ZnO NPs and Zn2+ ions by maize in order to further elucidate plant uptake pathways of ZnO NPs. The results demonstrate that the majority of Zn taken up was derived from Zn2+ released from ZnO NPs, and Zn accumulated in the form of Zn phosphate. ZnO NPs were observed mainly in the epidermis, a small fraction of ZnO NPs were present in the cortex and root tip cells, and some further entered the vascular system through the sites of the primary root-lateral root junction. However, no ZnO nanoparticle was observed to translocate to shoots, possibly due to the dissolution and transformation of ZnO NPs inside the plants.

Molecular-Scale Investigation with ESI-FT-ICR-MS on Fractionation of Dissolved Organic Matter Induced by Adsorption on Iron Oxyhydroxides

Adsorption by minerals is a common geochemical process of dissolved organic matter (DOM) which may induce fractionation of DOM at the mineral-water interface. Here, we examine the molecular fractionation of DOM induced by adsorption onto three common iron oxyhydroxides using electrospray ionization coupled with Fourier-transform ion cyclotron resonance mass spectrometry (ESI-FT-ICR-MS). Ferrihydrite exhibited higher affinity to DOM and induced more pronounced molecular fractionation of DOM than did goethite or lepidocrocite. High molecular weight (>500 Da) compounds and compounds high in unsaturation or rich in oxygen including polycyclic aromatics, polyphenols and carboxylic compounds had higher affinity to iron oxyhydroxides and especially to ferrihydrite. Low molecular weight compounds and compounds low in unsaturation or containing few oxygenated groups (mainly alcohols and ethers) were preferentially maintained in solution. This study confirms that the double bond equivalence and the number of oxygen atoms are valuable parameters indicating the selective fractionation of DOM at mineral and water interfaces. The results of this study provide important information for further understanding the behavior of DOM in the natural environment.

Adsorption of mercury on lignin: Combined surface complexation modeling and X-ray absorption spectroscopy studies

Adsorption of mercury (Hg) on lignin was studied at a range of pH values using a combination of batch adsorption experiments, a surface complexation model (SCM) and synchrotron X-ray absorption spectroscopy (XAS). Surface complexation modeling indicates that three types of acid sites on lignin surfaces, namely aliphatic carboxylic-, aromatic carboxylic- and phenolic-type surface groups, contributed to Hg(II) adsorption. The bond distance and coordination number of Hg(II) adsorption samples at pH 3.0, 4.0 and 5.5 were obtained from extended X-ray absorption fine structure (EXAFS) spectroscopy analysis. The results of SCM and XAS combined reveal that the predominant adsorption species of Hg(II) on lignin changes from HgCl(2)(0) to monodentate complex -C-O-HgCl and then bidentate complex -C-O-Hg-O-C- with increasing pH value from 2.0 to 6.0. The good agreement between SCM and XAS results provides new insight into understanding the mechanisms of Hg(II) adsorption on lignin.

In vitro biotransformation of PBDEs by root crude enzyme extracts: Potential role of nitrate reductase (NaR) and glutathione S-transferase (GST) in their debromination

In order to investigate the enzyme transformation of PBDEs and to track the key enzymes involved in PBDE degradation in plants, in vivo exposure of plants of ryegrass, pumpkin and maize and in vitro exposure of their root crude enzyme extracts to PBDEs were conducted. Degradation of PBDEs in the root crude enzyme solutions fit well with the first order kinetics (R(2)=0.52-0.97, P<0.05), and higher PBDEs degraded faster than the lower ones. PBDEs could be transformed to lower brominated PBDEs and hydroxylated-PBDEs by the root crude enzyme extracts with debromination as the main pathway which contributed over 90% of PBDE depletion. In vitro and in vivo exposure to PBDEs produced similar responses in root enzyme activities of which the nitroreductase (NaR) and glutathione-transferase (GST) activities decreased significantly, while the peroxidase, catalase and cytochrome P-450 activities had no significant changes. Furthermore, higher enzyme concentrations of NaR and GST led to higher PBDE debromination rates, and the time-dependent activities of NaR and GST in the root crude enzyme extracts were similar to the trends of PBDE depletion. All these results suggest that NaR and GST were the key enzymes responsible for PBDE degradation. This conclusion was further confirmed by the in vitro debromination of PBDEs with the commercial pure NaR and GST.

Transformation and Immobilization of Chromium by Arbuscular Mycorrhizal Fungi as Revealed by SEM–EDS, TEM–EDS, and XAFS

Arbuscular mycorrhizal fungi (AMF), ubiquitous soil fungi that form symbiotic relationships with the majority of terrestrial plants, are known to play an important role in plant tolerance to chromium (Cr) contamination. However, the underlying mechanisms, especially the direct influences of AMF on the translocation and transformation of Cr in the soil-plant continuum, are still unresolved. In a two-compartment root-organ cultivation system, the extraradical mycelium (ERM) of mycorrhizal roots was treated with 0.05 mmol L(-1) Cr(VI) for 12 days to investigate the uptake, translocation, and transformation of Cr(VI) by AMF using inductively coupled plasma mass spectrometry (ICP-MS), scanning electron microscopy equipped with energy-dispersive spectroscopy (SEM-EDS), transmission electron microscopy equipped with energy-dispersive spectroscopy (TEM-EDS), and X-ray-absorption fine structure (XAFS) technologies. The results indicated that AMF can immobilize quantities of Cr via reduction of Cr(VI) to Cr(III), forming Cr(III)-phosphate analogues, likely on the fungal surface. Besides this, we also confirmed that the extraradical mycelium (ERM) can actively take up Cr [either in the form of Cr(VI) or Cr(III)] and transport Cr [potentially in the form of Cr(III)-histidine analogues] to mycorrhizal roots but immobilize most of the Cr(III) in the fungal structures. Based on an X-ray absorption near-edge spectroscopy analysis of Cr(VI)-treated roots, we proposed that the intraradical fungal structures can also immobilize Cr within mycorrhizal roots. Our findings confirmed the immobilization of Cr by AMF, which plays an essential role in the Cr(VI) tolerance of AM symbioses.

Cellular internalization and intracellular biotransformation of silver nanoparticles in Chlamydomonas reinhardtii

Abstract It is necessary to elucidate cellular internalization and intracellular biotransformation in order to accurately assess the toxicity and fate of nanoparticles after interaction with organisms. Therefore, this work employed a combination of high resolution imaging and in situ detection spectroscopic techniques to systematically investigate the intracellular localization, morphology and chemical speciation of silver in the cells of Chlamydomonas reinhardtii, a unicellular freshwater green alga, after exposure to AgNPs coated with polyvinylpyrrolidone at a concentration of 2.0 mg/L. High resolution secondary ion mass spectrometry and high-angle annular dark field scanning transmission electron microscopy together with energy dispersive spectroscopy and selected area electron diffraction collectively confirmed that after 48 h of exposure, AgNPs entered the periplasmic space after cellular internalization into the algal cells. Silver was also found to coexist with sulfur inside the cytoplasm in both crystalline and amorphous forms, which were further identified as β-Ag2S and silver thiolates with synchrotron X-ray absorption spectroscopy. In combination, these analyses demonstrated that silver inside algae could be attributed to the uptake and sequestration of Ag+ ion released from AgNPs, which was further sequestrated into cellular compartments. This study provides solid evidence for particle internalization and biotransformation of AgNPs after interaction with algae.