Zhi Tang

Synthesis of magnetic metal-organic framework (MOF) for efficient removal of organic dyes from water

A novel, simple and efficient strategy for fabricating a magnetic metal-organic framework (MOF) as sorbent to remove organic compounds from simulated water samples is presented and tested for removal of methylene blue (MB) as an example. The novel adsorbents combine advantages of MOFs and magnetic nanoparticles and possess large capacity, low cost, rapid removal and easy separation of the solid phase, which makes it an excellent sorbent for treatment of wastewaters. The resulting magnetic MOFs composites (also known as MFCs) have large surface areas (79.52 m2 g−1), excellent magnetic response (14.89 emu g−1), and large mesopore volume (0.09 cm3 g−1), as well as good chemical inertness and mechanical stability. Adsorption was not drastically affected by pH, suggesting π–π stacking interaction and/or hydrophobic interactions between MB and MFCs. Kinetic parameters followed pseudo-second-order kinetics and adsorption was described by the Freundlich isotherm. Adsorption capacity was 84 mg MB g−1 at an initial MB concentration of 30 mg L−1, which increased to 245 mg g−1 when the initial MB concentration was 300 mg L−1. This capacity was much greater than most other adsorbents reported in the literature. In addition, MFC adsorbents possess excellent reusability, being effective after at least five consecutive cycles.

Sedimentary record of polycyclic aromatic hydrocarbons in Lake Erhai, Southwest China.

The temporal distribution of polycyclic aromatic hydrocarbons (PAHs) was investigated in a sediment core from Lake Erhai in Southwest China using gas-chromatography/mass spectrometry (GC/MS) method. The total organic carbon (TOC) normalized total PAHs concentrations (sum of US Environmental Protection Agency proposed 16 priority PAHs) ranged from 31.9 to 269 microg/g dry weight (dw), and were characterized by a slowly increasing stage in the deeper sediments and a sharp increasing stage in the upper sediments. The PAHs in the sediments were dominated by low molecular weight (LMW) PAHs, suggesting that the primary source of PAHs was low- and moderate temperature combustion processes. However, both the significant increase in high molecular weight (HMW) PAHs in the upper sediments and the vertical profile of diagnostic ratios pointed out a change in the sources of PAHs from low-temperature combustion to high-temperature combustion. The ecotoxicological assessment based on consensus-based sediment quality guidelines implied that potential adverse biological impacts were possible for benzo(ghi)perylenelene and most LMW PAHs. In addition, the total BaP equivalent quotient of seven carcinogenic polycyclic aromatic hydrocarbons (BaA, CHr, BbF, BkF, BaP, DBA and INP) was 106.1 ng/g, according to the toxic equivalency factors. Although there was no great biological impact associated with the HMW PAHs, great attention should be paid to these PAH components based on their rapid increase in the upper sediments.

Cetyltrimethylammonium Bromide-Coated Fe3O4 Magnetic Nanoparticles for Analysis of 15 Trace Polycyclic Aromatic Hydrocarbons in Aquatic Environments by Ultraperformance, Liquid Chromatography With Fluorescence Detection

Accurate determination of polycyclic aromatic hydrocarbons (PAHs) in surface waters is necessary for protection of the environment from adverse effects that can occur at concentrations which require preconcentration to be detected. In this study, an effective solid phase extraction (SPE) method based on cetyltrimethylammonium bromide (CTAB)-coated Fe3O4 magnetic nanoparticles (MNPs) was developed for extraction of trace quantities of PAHs from natural waters. An enrichment factor of 800 was achieved within 5 min by use of 100 mg of Fe3O4 MNPs and 50 mg of CTAB. Compared with conventional liquid-liquid extraction (LLE), C18 SPE cartridge and some newly developed methods, the SPE to determine bioaccessible fraction was more convenient, efficient, time-saving, and cost-effective. To evaluate the performance of this novel sorbent, five natural samples including rainwater, river waters, wastewater, and tap water spiked with 15 PAHs were analyzed by use of ultraperformance, liquid chromatography (UPLC) with fluorescence detection (FLD). Limits of determination (LOD) of PAHs (log Kow ≥ 4.46) ranged from 0.4 to 10.3 ng/L, with mean recoveries of 87.95 ± 16.16, 85.92 ± 10.19, 82.89 ± 5.25, 78.90 ± 9.90, and 59.23 ± 3.10% for rainwater, upstream and downstream river water, wastewater, and tap water, respectively. However, the effect of dissolved organic matter (DOM) on recovery of PAHs varied among matrixes. Because of electrostatic adsorption and hydrophobicity, DOM promoted adsorption of Fe3O4 MNPs to PAHs from samples of water from the field. This result was different than the effect of DOM under laboratory conditions. Because of competitive adsorption with the site of action on the surface of Fe3O4 MNPs for CTAB, recoveries of PAHs were inversely proportional to concentrations of Ca(2+) and Mg(2+). This novel sorbent based on nanomaterials was effective at removing PAHs at environmentally relevant concentrations from waters containing relevant concentrations of both naturally occurring organic matter and hardness metals.

Surfactant-modified flowerlike layered double hydroxide-coated magnetic nanoparticles for preconcentration of phthalate esters from environmental water samples

A novel type of layered, flowerlike magnetic double hydroxide (MLDH) nanoparticles modified by surfactants has been successfully synthesized and was applied as an effective sorbent for pre-concentration of several phthalate ester pollutants (PAEs) from water prior to quantification. The MLDH was obtained via a simple ultrasound-assisted method by using silica coated Fe3O4 as the core and anisotropic Mg-Al layered double hydroxide (Mg-Al LDH) nanocrystals as the shell to which analytes were absorbed. Orientation and dimensionality hierarchical structure as well as the large expandable interlayer free space and positive charge of the Mg-Al LDH shell make it easier to form anionic surfactant micelles on its surface via self-assembly. Due to its high adsorption area, compared with non-mesoporous nano solid-phase extraction agents, mesoporous channel shell and reduction diffusion path, MLDH exhibited high extraction efficiency of organic target residues. Under optimized conditions, with a total of 30mg of adsorbant added to from samples containing 400mL water from the environment recoveries of DPP, DBP, DCP and DOP were consistent with ranges of 69-101%, 79-101%, 86-102% and 63-100%, respectively. Standard deviations of recoveries ranged from 1 to 7%, respectively and the method was sensitive with limits of detection of 12.3, 18.7, 36.5 and 15.6ngL(-1). To the best of our knowledge, this is the first report of use of surfactant-modified MLDH nanoparticles and its application as adsorbent to pre-concentration of PAEs from environmental water samples prior to instrumental analyses.

Cu/Cu2O/CuO loaded on the carbon layer derived from novel precursors with amazing catalytic performance.

A simple, novel method for synthesis of Cu/Cu2O/CuO on surfaces of carbon (Cu/Cu2O/CuO@C) as a non-noble-metal catalyst for reduction of organic compounds is presented. Compared with noble metals, Cu/Cu2O/CuO@C particles are more efficient and less expensive. Characterization of the Cu/Cu2O/CuO@C composites by high-resolution transmission electron microscope (HRTEM), x-ray diffraction (XRD), infrared spectroscopy and Raman analysis, revealed that it was composed of graphitized carbon with numerous nanoparticles (100nm in diameter) of Cu/CuO/Cu2O that were uniformly distributed on internal and external surfaces of the carbon support. Gallic acid (GA) has been used as both organic ligand and carbon precursor with metal organic frameworks (MOFs) as the sacrificial template and metal oxide precursor in this green synthesis. The material combined the advantages of MOFs and Cu-containing materials, the porous structure provided a large contact area and channels for the pollutions, which results in more rapid catalytic degradation of pollutants and leads to greater efficiency of catalysis. The material gave excellent catalytic performance for organic dyes and phenols. In this study, Cu/Cu2O/CuO@C was used as catalytic to reduce 4-NP, which has been usually adopted as a model reaction to check the catalytic ability. Catalytic experiment results show that 4-NP was degraded approximately 3min by use of 0.04mg of catalyst and the conversion of pollutants can reach more than 99%. The catalyst exhibited little change in efficacy after being utilized five times. Rates of degradation of dyes, such as Methylene blue (MB) and Rhodamine B (RhB) and phenolic compounds such as O-Nitrophenol (O-NP) and 2-Nitroaniline (2-NA) were all similar.

Effects of monovalent and divalent metal cations on the aggregation and suspension of Fe3O4 magnetic nanoparticles in aqueous solution.

There has been limited research investigating how the mechanisms of aggregation of magnetic nanoparticles (MNPs) are affected by inorganic ions. In this study, Na+, Mg2+, Ca2+, Sr2+ and Ba2+ were selected to systematically study the aggregation mechanisms of Fe3O4 MNPs. The results indicated that divalent cations more significantly affected the stabilities of MNPs than Na+ at low concentrations (e.g., 0.1mM) in a decreasing order of Ba2+>Sr2+>Ca2+>Mg2+>Na+. Extended DLVO theory did not offer a satisfactory explanation for the above difference due because it ignores specific ion effects. It was also found that the initial adsorption ratios of these metals by Fe3O4 MNPs were linearly proportional to the hydrodynamic diameter (HDD) of Fe3O4 MNPs before aggregation occurred. In addition to the valence states, the hydration forces and ionic radii of the metal cations were proposed to be other factors that significantly affected the interactions of metal cations with Fe3O4 MNPs based on the excellent linear relationships of the HDD of Fe3O4 MNPs and these three factors. Moreover, a bridging function of divalent cations might develop after aggregation occurred based on the increases in their adsorption amounts and intensities for binding oxygen-containing functional groups. In addition, an increase in the positive ζ potential of MNPs was observed with the addition of divalent cations until 10.0mM at a pH of 5.0, which potentially enhances the resistance of MNPs to aggregation in aquatic systems compared with Na+. Consequentially, the effects of metal cations on the aggregation of MNPs are determined by the hydration forces, valance states, ionic radii and bond types formed on the MNPs. Thus, the specific ion effects of these cations should be considered in predicting the environmental behaviors of specific nanomaterials.

Amendment of water quality standards in China: viewpoint on strategic considerations

Water quality standards (WQS) are the most important tool for protection of quality of aquatic environments in China and play a decisive role in the management of China’s aquatic environments. Due to limited scientific information available previously, WQS were developed largely based on water quality criteria (WQC) or WQS recommended by developed countries, which may not be suitable for current circumstances in China. The Chinese government recently initiated the revision of Environmental Quality Standards for Surface Water (EQSSW) (GB3838-2002) to meet the challenge of environmental protection. This review analyzed how the WQS developed and applied in China differ from those of more developed countries and pointed out that the lack of strong scientific bases for China’s WQC pose major limitations of current WQS. We focus on discussing the six aspects that require high attention on how to establish a national WQC system to support the revision of WQS (Table 1) such as development of methodology, refining water function zoning, establish priority pollutants list, improving protection drinking water sources, development of site-specific water quality criteria, and field toxicity test. It is essential that China and other developing countries established a relatively mature system for promulgating, applying, and enforcing WQC and to implement a dynamic system to incorporate most recent research results into periodically updated WQS.

Historical record of effects of human activities on absolute and relative concentrations of Polycyclic aromatic hydrocarbons (PAHs) in Lake Chao, China

Polycyclic aromatic hydrocarbons(PAHs)are attracting concern because of their potential toxicity,posing serious threats to health of humans and ecosystems(Kim et al.,2013;Zhao et al.,2016).Generally,similar to other contaminants’behaviors(Wu et al.,2001;Zhang et al.,2007,2008;Lu et al.,2009),PAHs result from natural organic matter and activities of humans,the latter’s contribution usually outweighing the inputs from other sources(Fernandez et al.,2000;Srogi,2007).

Magnetic Nanoparticles Interaction with Humic Acid: In the Presence of Surfactants

Adsorbed humic acid (HA) on surfaces of nanoparticles (NPs) will affect their transport, transfer, and fate in the aquatic environment, especially in the presence of surfactants, and thereby potentially alter exposures and bioavailable fractions of NPs and surfactants. This study investigated adsorption of HA on Fe3O4 NPs in the presence or absence of surfactant. Surfactant established a bridge connecting HA and Fe3O4 NPs, and significantly changed adsorption behavior of HA on NPs. Adsorption of HA in the absence of surfactant was 120.3 mg/g, but 350.0 mg/g and 146.5 mg/g in the present of CTAB (hexadecyl trimethylammonium bromide) and SDS (sodium dodecyl sulfate), respectively. Surfactants can form different stages (hemimicelles, mixed hemimicelles and admicelles) on Fe3O4 NPs by electrostatic and hydrophobic interactions, adsorption of HA was different for each of those stages. Adsorption of HA on surface of Fe3O4 NPs/CTAB was codetermined by hydrophobic, electrostatic interactions and ligand exchange. The presence of CTAB or SDS changed mechanisms for adsorption and effects of functional groups. Results of Fourier transform infrared (FTIR) and X-ray photoelectron spectroscopy (XPS) indicated that carbohydrate carbon was important in adsorption of HA on Fe3O4 NPs in the presence of surfactants.

Fluorescence regional integration and differential fluorescence spectroscopy for analysis of structural characteristics and proton binding properties of fulvic acid sub-fractions

Structural characteristics and proton binding properties of sub-fractions (FA3-FA13) of fulvic acid (FA), eluted stepwise by pyrophosphate buffer were examined by use of fluorescence titration combined with fluorescence regional integration (FRI) and differential fluorescence spectroscopy (DFS). Humic-like (H-L) and fulvic-like (F-L) materials, which accounted for more than 80% of fluorescence response, were dominant in five sub-fractions of FA. Based on FRI analysis, except the response of F-L materials in FA9 and FA13, maximum changes in percent fluorescence response were less than 10% as pH was increased from 2.5 to 11.5. Contents of carboxylic and phenolic groups were compared for fluorescence peaks of FA sub-fractions based on pH-dependent fluorescence derived from DFS. Static quenching was the dominant mechanism for binding of protons by FA sub-fractions. Dissociation constants (pKa) were calculated by use of results of DFS and the modified Stern-Volmer relationship. The pKa of H-L, F-L, tryptophan-like and tyrosine-like materials of FA sub-fractions exhibited ranges of 3.17-4.06, 3.12-3.97, 4.14-4.45 and 4.25-4.76, respectively, for acidic pHs. At basic pHs, values of pKa for corresponding materials were in ranges of 9.71-10.24, 9.62-10.99, 9.67-10.31 and 9.33-10.28, respectively. At acidic pH, protein-like (P-L) materials had greater affinities for protons than did either H-L or F-L materials. The di-carboxylic and phenolic groups were likely predominant sites of protonation for both H-L and F-L materials at both acidic and basic pHs. Amino acid groups were significant factors during proton binding to protein-like materials of FA sub-fractions at basic pH.