Complex interplay between formation routes and natural organic matter modification controls capabilities of C60 nanoparticles (nC60) to accumulate organic contaminants

Accumulation of organic contaminants on fullerene nanoparticles (nC₆₀) may significantly affect the risks of C₆₀ in the environment. The objective of this study was to further understand how the interplay of nC₆₀ formation routes and humic acid modification affects contaminant adsorption of nC₆₀. Specifically, adsorption of 1,2,4,5-tetrachlorobenzene (a model nonionic, hydrophobic organic contaminant) on nC₆₀ was greatly affected by nC₆₀ formation route – the formation route significantly affected the aggregation properties of nC₆₀, thus affecting the available surface area and the extent of adsorption via the pore-filling mechanism. Depending on whether nC₆₀ was formed via the “top-down” route (i.e., sonicating C₆₀ powder in aqueous solution) or “bottom-up” route (i.e., phase transfer from an organic solvent) and the type of solvent involved (toluene versus tetrahydrofuran), modification of nC₆₀ with Suwannee River humic acid (SRHA) could either enhance or inhibit the adsorption affinity of nC₆₀. The net effect depended on the specific way in which SRHA interacted with C₆₀ monomers and/or C₆₀ aggregates of different sizes and morphology, which determined the relative importance of enhanced adsorption from SRHA modification via preventing C₆₀ aggregation and inhibited adsorption through blocking available adsorption sites. The findings further demonstrate the complex mechanisms controlling interactions between nC₆₀ and organic contaminants, and may have significant implications for the life-cycle analysis and risk assessment of C₆₀.     

Green synthesis, characterization and antimicrobial activity of silver nanoparticles using methanolic root extracts of Diospyros sylvatica

The current research study focuses to formulate the biosynthesized silver nanoparticles for the first time from silver acetate using methanolic root extracts of Diospyros sylvatica, a member of family Ebenaceae. TEM analysis revealed the average diameter of Ag NPs around 8 nm which is in good agreement with the average crystallite size (10 nm) calculated from X-ray Diffraction (XRD) analysis. Further the study has been extended to the antimicrobial activity against test pathogenic Gram (+) ve, Gram (−) ve bacterial and fungal strains. The bioinspired Ag-NP showed promising activity against all the tested bacterial strains and the activity was enhanced with increased dosage levels.     

Bioaccumulation and effects of sediment-associated gold- and graphene oxide nanoparticles on Tubifex tubifex

With the development of nanotechnology,gold(Au) and graphene oxide(GO) nanoparticles have been widely used in various fields,resulting in an increased release of these particles into the environment.The released nanoparticles may eventually accumulate in sediment,causing possible ecotoxicological effects to benthic invertebrates.However,the impact of Au-NPs and GO-NPs on the cosmopolitan oligochaete,Tubifex tubifex,in sediment exposure is not known.Mortality,behavioral impact(GO-NP and Au-NP) and uptake(only Au-NP) of sediment-associated Au-NPs(4.9±0.14 nm) and GO-NPs(116±0.05 nm) to T.tubifex were assessed in a number of 5-day exposure experiments.The results showed that the applied Au-NP concentrations(10 and 60 μg Au/g dry weight sediment) had no adverse effect on T.tubifex survival,while Au bioaccumulation increased with exposure concentration.In the case of GO-NPs,no mortality of T.tubifex was observed at a concentration range of 20 and180 μg GO/g dry weight sediment,whereas burrowing activity was significantly reduced at 20 and 180 μg GO/g dry weight sediment.Our results suggest that Au-NPs at 60 μg Au/g or GO-NPs at 20 and 180 μg GO/g were detected by T.tubifex as toxicants during short-term exposures.     

Synthesis, characterization and application of Lagerstroemia speciosa embedded magnetic nanoparticle for Cr(VI) adsorption from aqueous solution

Lagerstroemia speciosa bark (LB) embedded magnetic nanoparticles were prepared by co-precipitation of Fe²⁺ and Fe³⁺ salt solution with ammonia and LB for Cr(VI) removal from aqueous solution. The native LB, magnetic nanoparticle (MNP), L. speciosa embedded magnetic nanoparticle (MNPLB) and Cr(VI) adsorbed MNPLB particles were characterized by SEM–EDX, TEM, BET-surface area, FT-IR, XRD and TGA methods. TEM analysis confirmed nearly spherical shape of MNP with an average diameter of 8.76 nm and the surface modification did not result in the phase change of MNP as established by XRD analysis, while led to the formation of secondary particles of MNPLB with diameter of 18.54 nm. Characterization results revealed covalent binding between the hydroxyl group of MNP and carboxyl group of LB particles and further confirmed its physico-chemical nature favorable for Cr(VI) adsorption. The Cr(VI) adsorption on to MNPLB particle as an adsorbent was tested under different contact time, initial Cr(VI) concentration, adsorbent dose, initial pH, temperature and agitation speed. The results of the equilibrium and kinetics of adsorption were well described by Langmuir isotherm and pseudo-second-order model, respectively. The thermodynamic parameters suggest spontaneous and endothermic nature of Cr(VI) adsorption onto MNPLB. The maximum adsorption capacity for MNPLB was calculated to be 434.78 mg/g and these particles even after Cr(VI) adsorption were collected effortlessly from the aqueous solution by a magnet. The desorption of Cr(VI)-adsorbed MNPLB was found to be more than 93.72% with spent MNPLB depicting eleven successive adsorption–desorption cycles.     

单层硅烷负载磁铁矿纳米颗粒的制备及除磷性能

研究了N-氨乙基-γ-氨丙基三甲氧基硅烷在水溶液中以单层形式负载于磁铁矿纳米颗粒表面的方法,并研究了单分子层硅烷负载磁铁矿纳米颗粒吸附剂(monolayer of silane on magnetite nanoparticles,MSMNPs)的除磷性能.结果表明,在低浓度下(平衡浓度小于300 mg·L~(-1))硅烷在磁铁矿纳米颗粒表面产生单层吸附,而反应温度90℃以上或离子强度0.1 mol·L~(-1)NaCl以上可以使单层硅烷在磁铁矿纳米颗粒表面的覆盖度达到~100%.FTIR和XPS图谱显示负载的硅烷以化学键的形式与磁铁矿纳米颗粒表面相结合.单层硅烷负载不引起磁性强度的明显变化.MSMNPs对磷的吸附等温线更符合Langmuir模型,拟合得到的最大吸附量为7.59 mg·g~(-1).由于磷吸附位位于MSMNPs的最外面,磷的吸附及脱附均很快,30 min内达到90%以上,1 h内达到平衡.因此,MSMNPs是一种易分离因而可反复使用,并且可快速吸附与脱附污染物的新型吸附剂.     

纳米磁性磷酸二氢钙对Cd的吸附、回收与再生

以Ca（H₂PO₄）₂、铁盐与亚铁盐为原料,采用共沉淀法制备成纳米磁性材料Ca（H₂PO₄）₂@Fe₃O₄（NMCDP）,研究其对Cd²⁺的吸附、回收与再生效果.透射电镜（TEM）、红外光谱（FTIR）、X射线衍射（XRD）显示,NMCDP粒径约60 nm,稳定性良好,饱和磁化强度为30.9 emu·g^-1.吸附动力学表明,NMCDP对Cd²⁺的吸附1 h之内即可达到平衡,符合准二级动力学模型.吸附热力学表明,NMCDP对Cd²⁺的吸附符合Langmuir与Freundlich等温吸附模型,最大吸附量为142.50 mg·g^-1.在pH值由2增加到3时,吸附量随溶液初始pH值的升高而增加,当pH值大于3后,逐渐保持稳定;溶液中共存离子Na⁺、Mg²⁺、Cu²⁺对材料吸附Cd²⁺均有一定的影响,影响程度Cu²⁺ > Mg²⁺ > Na⁺.采用0.01 mol·L^-1 HCl与EDTA-Na₂均可解吸出部分吸附的Cd²⁺,以EDTA-Na₂解吸率较高,达到68%,从而实现NMCDP的再生.     

Hierarchical Ag-SiO2@Fe3O4 magnetic composites for elemental mercury removal from non-ferrous metal smelting flue gas

Hierarchical Ag-SiO_2@Fe_3O_4 magnetic composites were selected for elemental mercury(Hg~0) removal from non-ferrous metal smelting flue gas in this study. Results showed that the hierarchical Ag-SiO_2@Fe_3O_4 magnetic composites had favorable Hg~0 removal ability at low temperature. Moreover, the adsorption capacity of hierarchical magnetic composite is much larger than that of pure Fe_3O_4 and SiO_2@Fe_3O_4. The Hg~0 removal efficiency reached the highest value as approximately 92% under the reaction temperature of 150°C, while the removal efficiency sharply reduced in the absence of O_2. The characterization results indicated that Ag nanoparticles grew on the surface of SiO_2@Fe_3O_4 support. The large surface area of SiO_2 supplied efficient reaction room for Hg and Ag atoms. Ag–Hg amalgam is generated on the surface of the composites. In addition, this magnetic material could be easily separated from fly ashes when adopted for treating real flue gas, and the spent materials could be regenerated using a simple thermal-desorption method.     

Applications of magnetic nanoparticles in surface-enhanced Raman scattering (SERS) detection of environmental pollutants

Environmental pollution, a major problem worldwide, poses considerable threat to human health and ecological environment. Efficient and reliable detection technologies, which focus on the appearance of emerging environmental and trace pollutants, are urgently needed. Surface-enhanced Raman scattering(SERS) has become an attractive analytical tool for sensing trace targets in environmental field because of its inherent molecular fingerprint specificity and high sensitivity. In this review, we focused on the recent developments in the integration of magnetic nanoparticles(MNPs) with SERS for facilitating sensitive detection of environmental pollutants. An overview and classification of different types of MNPs for SERS detection were initially provided, enabling us to categorize the huge amount of literature that was available in the interdisciplinary research field of MNPs based SERS technology. Then, the basic working principles and applications of MNPs in SERS detection were presented. Subsequently, the detection technologies integrating MNPs with SERS that eventually were used for the detection of various environmental pollutions were reviewed. Finally, the advantages of MNP-basedSERS detection technology for environmental pollutants were concluded, and the current challenges and future outlook of this technology in practical applications were highlighted. The application of the MNPsbasedSERS techniques for environmental analysis will be significantly advanced with the great progresses of the nanotechnologies, optics, and materials.     

A mechanistic study of ciprofloxacin adsorption by goethite in the presence of silver and titanium dioxide nanoparticles

The adsorption behaviors of ciprofloxacin (CIP), a fluoroquinolone antibiotic, onto goethite (Gt) in the presence of silver and titanium dioxide nanoparticles (AgNPs and TiO₂NPs) were investigated. Results showed that CIP adsorption kinetics in Gt with or without NPs both followed the pseudo-second-order kinetic model. The presence of AgNPs or TiO₂NPs inhibited the adsorption of CIP by Gt. The amount of inhibition of CIP sorption due to AgNPs was decreased with an increase of solution pH from 5.0 to 9.0. In contrast, in the presence of TiO₂NPs, CIP adsorption by Gt was almost unchanged at pHs of 5.0∼6.5 but was decreased with an increase of pH from 6.5 to 9.0. The mechanisms of AgNPs and TiO₂NPs in inhibiting CIP adsorption by Gt were different, which was attributed to citrate coating of AgNPs resulting in competition with CIP for adsorption sites on Gt, while TiO₂NPs could compete with Gt for CIP adsorption. Additionally, CIP was adsorbed by Gt or TiO₂NPs through a tridentate complex involving the bidentate inner-sphere coordination of the deprotonated carboxylic group and hydrogen bonding through the adjacent carbonyl group on the quinoline ring. These findings advance our understanding of the environmental behavior and fate of fluoroquinolone antibiotics in the presence of NPs.     

Estimating the relevance of engineered carbonaceous nanoparticle facilitated transport of hydrophobic organic contaminants in porous media

Naturally occurring nanoparticles (NP) enhance the transport of hydrophobic organic contaminants (HOCs) in porous media. In addition, the debate on the environmental impact of engineered nanoparticles (ENP) has become increasingly important. HOC bind strongly to carbonaceous ENP. Thus, carbonaceous ENP may also act as carriers for contaminant transport and might be important when compared to existing transport processes. ENP bound transport is strongly linked to the sorption behavior, and other carbonaceous ENP-specific properties. In our analysis the HOC-ENP sorption mechanism, as well as ENP size and ENP residence time, was of major importance. Our results show that depending on ENP size, sorption kinetics and residence time in the system, the ENP bound transport can be estimated either as (1) negligible, (2) enhancing contaminant transport, or (3) should be assessed by reactive transport modeling. One major challenge to this field is the current lack of data for HOC-ENP desorption kinetics.