The effect of heavy precipitation on the leaching of heavy metals from tropical coastal legacy tailings.

The continued growth in demand for mineral resources has led to a large amount of mining wastes, which is a major challenge in the context of carbon neutrality and climate change. In this study, runoff migration, batch leaching, and column experiments were used to investigate the short-, medium-, and long-term leaching of heavy metals from legacy tailings, respectively; the cumulative metal release kinetic equations were established, and the long-term effects of tailings leaching were verified by HYDRUS-1D. In runoff migration experiments, surface dissolution of tailings and the co-migration of adsorbed soil particles by erosion were the main carriers in the early stages of leachate formation (Mn âˆ¼ 65 mg/L and SO42- up to 2697.2 mg/L). Batch leaching tests showed that the concentration of heavy metals in soil leached by acid rain were 0.1 âˆ¼ 22.0 µg/L for Cr, 0.7 âˆ¼ 26.0 µg/L for Cu, 4.8 âˆ¼ 5646.0 µg/L for Mn, 0.3 âˆ¼ 232.4 µg/L for Ni, and 1.3 âˆ¼ 448.0 µg/L for Zn. The results of column experiments indicated that some soluble components and metals with high mobility showed a significant decreasing trend at cumulative L/S ≤ 2. Additionally, the metals have higher leaching rates under TCLP conditions, as shown by Mn > Co > Zn > Cd > Ni > Cu > Pb > Cr. The fitting results of Langmuir equation were closer to the cumulative release of metals in the real case, and the release amounts of Mn, Zn, Co, and Ni were higher with 55, 5.84, 2.66, and 2.51 mg/kg, respectively. The water flow within tailings affects the spatial distribution of metals, which mainly exist in relatively stable chemical fractions (F3 + F4 + F5 > 90 %) after leaching. Numerical simulation verified that Mn in leachate has reached 8 mg/L at a scale of up to 100 years. The research results are expected to provide technical basis for realizing the resource utilization of tailings in the future.

Metal distribution behavior based on soil aggregate size in a post-restoration coastal mining area.

Soil aggregate size plays an important role in controlling the distribution and transport of metals. Metals immobilized in soil particles will pose potential risks through production/sink flow and infiltration. This study explored the distribution behavior of metals based on soil aggregate size in a restored coastal mining area by establishing Structural Equation Model (SEM) and column experiments. The results showed that hydrological factors and a high degree of weathering accelerated the dissolution of metals from the mine, the desorption of Wa-NH4+-N, the release of F-, and the leaching of NO3-. Driven by soil properties, natural factors, and anthropogenic activities, the total metal content (Totalmetal) of Cr, Ni, Zn, Mn, and As showed significant spatial heterogeneity compared to Cd, Co, Cu, and Pb. The geochemical fraction of metals (Geometal) indicated that Cd, Co, Pb, Zn, As, and Cu are mainly present in iron­manganese oxidation bound, organically bound, and residual fractions. The results of SEM showed that the physicochemical properties, Wa-NH4+-N, nitrate nitrogen, and inorganic anions of the soil could explain 69.1 %, 76.4 %, 97.1 %, and 80.0 % of the variation in Kd-Mn, Kd-Pb, Kd-Ni, and Kd-Zn, respectively. While Kd-Cd, Kd-Cu, and Kd-Cr could be predicted by the Totalmetal, but the Geometal seemed to have little influence on metal Kd. The results of column experiments showed that macroaggregates (>0.25 mm) significantly affected the distribution of Co, Cr, Cu, Mn, Ni, Pb, and Zn in the topsoil. The severe disruption of soil aggregate structure resulted in small fluctuations of anthropogenic Cu, Mn, Pb, Zn, and As in different layers of deep soil. In addition, mineral composition in >0.15 mm particle size was more likely to change. Overall, the hydrological cycle of coastal mines increases the uncertainty of their response to risk. Our study provides a basis for future strategies for priority control and risk prevention.

One-step synthesis of nitrogen-functionalized graphene aerogel for efficient removal of hexavalent chromium in water.

The efficient removal of hexavalent chromium (Cr(VI)) with high toxicity has attracted widespread concern since it causes serious harm to ecological environment and public health. Herein, we report a novel nitrogen-functionalized graphene aerogel with stereoscopic structure through a simple hydrothermal method and freeze drying for Cr(VI) removal from water. Graphene oxide (GO) and nitrogenous organics polyethyleneimine (PEI) and pyrrole are used as raw materials for preparing PEI/polypyrrole/GO aerogel (PPGA) adsorbent. PEI and pyrrole act as nitrogen sources to introduce nitrogenous functional groups, and also take on the role of cross-linkers for helping GO sheets to form stereoscopic structure. The obtained PPGA has a fast adsorption rate, excellent reusability, and shows a remarkable adsorption capacity for Cr(VI) up to 458.24 mg/g under the optimal conditions (pH 2.0, 298 K, Cr(VI): 600 mg/L, dosage: 0.4 g/L). The adsorption process of Cr(VI) on PPGA can fit the pseudo-second-order kinetic model well. Analysis of intraparticle diffusion shows that the Cr(VI) removal process is a multi-step process. Adsorption thermodynamic and isotherm results demonstrate Cr(VI) adsorption on PPGA is a spontaneous endothermic process. The adsorption mechanism involves electrostatic attraction, redox, and chelation. In general, this work provides a simple and eco-friendly way to prepare PPGA, which has a great potential for actual application of Cr(VI) removal in effluent.

Efficient removal of Cr(VI) by a 3D Z-scheme TiO2-ZnxCd1-xS graphene aerogel via synergy of adsorption and photocatalysis under visible light.

Efficient and robust photocatalysts for environmental pollutants removal with outstanding stability have great significance. Herein, we report a kind of three dimensional (3D) photocatalyst presented as Z-scheme heterojunction, which combining TiO2 and ZnxCd1-xS with graphene aerogel to contrast TiO2-ZnxCd1-xS graphene aerogel (TSGA, x=0.5) through a moderate hydrothermal process. The as-prepared Z-scheme TSGA was used to remove aqueous Cr(VI) via a synergistic effect of adsorption and visible light photocatalysis. The adsorption equilibrium can be reached about 40 min, then after about 30 min irradiation under visible light (wavelength (λ) > 420 nm) the removal rate of Cr(VI) almost reached 100%, which is much better than the performance of pristine TiO2 and Zn0.5Cd0.5S, as well as TiO2 graphene aerogel (TGA) and Zn0.5Cd0.5S graphene aerogel (SGA). The virulent Cr(VI) was reduced to Cr(III) with hypotoxicity after photocatalysis on TSGA, meanwhile the as-synthesized TSGA presented a good stability and reusability. The reduced graphene oxide (rGO) sheets between TiO2 and Zn0.5Cd0.5S played a role as charge transfer mediator, promoting the photoinduced electrons transfer and photocatalysis ability of TSGA was enhanced significantly. Hence, such photocatalyst exhibits a potential application on removing heavy metals with high efficiency and stability from polluted aqueous environment.

Enhanced removal of Cr(VI) from aqueous solutions by polymer-mediated nitrogen-rich reduced graphene oxide.

The efficient removal of heavy metal by rationally designed carbon-based adsorbents is a key challenge in the field of water purification. Herein, we report a nitrogen-enriched lignosulfonate exfoliated graphene oxide (N-LEGO) for hexavalent chromium (Cr(VI)) removal from aqueous solution. The nitrogen content of N-LEGO reached 13.28%, and the ratio of N-bonding configurations (pyri-N:amine-N:pyrro-N:grap-N) was 2.3:1.6:1:2.3. For Cr(VI) with initial concentration of 70 mg L-1 under pH= 2, the residuary concentration after treated by N-LEGO was close to 0.004 mg L-1, which meets the industrial wastewater discharge standard. The Cr(VI) adsorption behavior on N-LEGO can be fitted with the pseudo-second-order kinetics and Freundlich isotherm model well. The adsorption mechanism of Cr(VI) on N-LEGO includes anions electrostatic attraction, reduction and surface chelation. Density functional theory (DFT) simulations showed that N atoms doping was feasible and thermodynamically stable, meanwhile the N-doped system was easier to adsorb Cr2O72- than HCrO4-. The findings of this work can provide a new idea for the development of N-doped carbon-based adsorbents for the removal of highly toxic Cr(VI) from aqueous solutions.

Surface oxygen vacancies and carbon dopant co-decorated magnetic ZnFe2O4 as photo-Fenton catalyst towards efficient degradation of tetracycline hydrochloride.

Carbon doped strategy has been recognized as an efficient strategy to enhance photo-Fenton degradation performance. However, the preparation of high efficiency C-doped photocatalyst has been a significant challenge. Herein, we synthesized magnetic carbon-doped ZnFe2O4 via a facile solvothermal-calcination route. The photo-Fenton activity of C-doped ZnFe2O4 under visible light (λ > 420 nm) was evaluated by degradation of tetracycline hydrochloride. C-doped sample, CZF-2 (0.5 g L-1) presented excellent removal performance for TC-HCl (20 mg L-1) in presence of H2O2 (10 mM) and could remove 90.8% of TC-HCl within 50 min. The C-doping modulates crystal defects and generates surface oxygen vacancies simultaneously, thus building a new C-doping level near valence band and a defect level under the conduction band. Meanwhile, surface oxygen vacancies bring photo-generated electrons and electrons generated from itself to surface to accelerate photo-Fenton reaction, and the holes are rapidly transferred to the surface to participate in the degradation of pollutants.

Hierarchical health risk assessment and influence factors of an ecological post-restoration oil shale mining area based on metal bioavailability.

The environmental problems caused by mining are continuous and multifaceted, in order to help manage and plan restored mining areas, the bioavailability of metals is an effective tool for measuring the potential risks to human health. This study analyzes the geochemical fractions of eight metals (As, Cd, Cr, Cu, Mn, Ni, Pb, and Zn) to compare their bioavailability and establishes a Hierarchical health risk (HHR) model to assess the human health risks of the mine area after restoration. The results indicated that children have the highest non-carcinogenic risks exposed through ingestion (HI-ingestion) due to their special behaviors; HI-dermal may be enriched in the body; and HI-inhalation is lowest, as it is related to soil particle size. Affected by local economic development, environmental climate, soil type, and mining, the carcinogenic risk of exposure through the skin (CR-dermal) for adults significantly exceeds the acceptable safety level (ASL). The spatial distribution shows that the harm of mining to human health is a continuous process. There was still a significant CR for adults after remediation, and the HI of tailings exposure was more serious. The Classification and Regression Tree (CART) model of metal bioavailability was developed by integrating the extrinsic and intrinsic factors of metals to explore the effects of different factors on metal bioavailability and predict. The results showed that the bioavailability of metals was a dynamic process that combined land use, the distance to traffic roads, physicochemical properties of soil, and geochemical fractions of metal, and that it affects human health both directly and indirectly. Due to the fragility and sensitivity of the ecosystem after the mining area is restored, it may face greater environmental health risks.

Integrated ecological risk assessment of heavy metals in an oil shale mining area after restoration.

Although the mining area has been restored, the environmental problems caused by years of large-scale oil shale mining are still continuing, coupled with the intensive distribution of the surrounding petrochemical industry, posing a serious threat to the local ecological environment. In this study, we investigated eight heavy metals (Cu, Ni, Pb, Cd, As, Cr, Mn and Zn) contamination and distribution around mining area, evaluated the potential risks of environment, identified the main sources of metal pollution and performed source apportionment. The results showed that the original north and south dumps were seriously polluted, and the CF values were significantly higher than other sampling sites. Ni, Zn and Mn have high coefficients of variation, which may be greatly affected by human factors and especially the waste slag piled up. The concentration of heavy metals in the water was lower than in the soil; soil particles, pH, Eh and acid mine drainage influence the variation of heavy metal concentrations. As and Cd have very high RAC values, and accordingly they were mainly present in the exchangeable and reduced fractions. Mn was exposed to higher ecological risks, followed by Pb, although there were high loads on carbonate bound and oxidizable fractions. APCS-MLL receptor model was used to identify and apportionment three main sources of contamination. The mean contribution rates of industrial activity, atmospheric deposition and mixed sources accounted for 39.77%, 22.24% and 37.99%, respectively. Cluster analysis further classified the metal pollution sources according to the spatial distance of sampling points.

Enhanced removal of toxic hexavalent chromium from aqueous solution by magnetic Zr-MOF@polypyrrole: performance and mechanism.

Magnetic Zr-based metal organic framework (UiO-66) @Polypyrrole (magnetic UiO-66@Ppy) was prepared to eliminate Cr(VI) from water. SEM and TEM results clearly revealed that the magnetic UiO-66@Ppy was a core-double-shell structure with the core of Fe3O4, inner shell UiO-66, and outer shell Ppy. The introduction of zirconium MOFs UiO-66 effectively prevented the agglomeration of polypyrrole and provided more available adsorption sites, the surface area increased from 9.57 m2/g (Ppy) to 10.57 m2/g (Fe3O4@Ppy) and 52.49 m2/g (magnetic UiO-66@Ppy). The magnetic UiO-66@Ppy possessed a high adsorption capacity of 259.1 mg/g in removing Cr(VI) from water. Adsorption kinetics followed the pseudo-second-order model. The removal of Cr(VI) involved the following mechanisms: (1) electrostatic attraction and ions exchange, the HCrO4- was adsorbed on the surface of magnetic UiO-66@Ppy by the protonated N(PpyN+) and Cl-; (2) reduction, Cr(VI) was reduced to Cr(III) by the reductive functional group(-NH-); (3) chelation, Cr(III) was immobilized on adsorbent by amine groups.

Leaching characteristics of heavy metals in tailings and their simultaneous immobilization with triethylenetetramine functioned montmorillonite (TETA-Mt) against simulated acid rain.

For further understanding leaching characteristics of heavy metals in tailings and better immobilization on heavy metals against acid rain, batch experiments were conducted. The leaching results of Cu(II), Zn(II), Cd(II) and Mn(II) can be well fit by second-order kinetics equation, and Pb(II) can be well fit by two-constant equation. The leaching intensity of heavy metals in tailings was ranged as: Mn(II)> Cu(II)> Cd(II)> Zn(II)> Pb(II). Triethylenetetramine functioned montmorillonite (TETA-Mt) was successfully synthesized and can obtain simultaneous immobilization effect compared with Mt and TETA, and immobilization rates on Cu(II), Cd(II), Mn(II) and Zn(II) can reach above 90%, the immobilization rate on Pb(II) can reach more than 75%. The mechanisms for efficient immobilization of heavy metals on TETA-Mt included buffering and adsorption abilities. The mechanism for TETA-Mt adsorption of heavy metals included physical absorption, chelation and chemical sedimentation. The results showed that TETA-Mt can be applied to effective immobilization of heavy metals in tailings and efficient remediation of acid mine drainage (AMD) in acid rain area.

Adhesion of Sphingomonas sp. GY2B onto montmorillonite: A combination study by thermodynamics and the extended DLVO theory.

Bacterial adhesion on mineral surface are of fundamental importance in geochemical processes and biogeochemical cycling, such as mineral transformation and clay-mediated biodegradation. In this study, thermodynamics analysis combined with classical Derjaguin-Landau-Verwey-Overbeek (DLVO) theory as well as the extended DLVO (XDLVO) theory were employed to investigate the adhesion of the Gram-negative PAH-degrading bacteria Sphingomonas sp. GY2B on montmorillonite (Mt). Scanning electron microscopy (SEM), Fourier transform infrared spectra (FTIR) and X-ray photoelectron spectroscopy (XPS) indicated the affinity of GY2B for Mt, and the experimental results could be described well by pseudo-second-order (R2 = 0.997) and Langmuir model (R2 = 0.995). The thermodynamics analysis revealed the physical nature of bacterial adhesion onto Mt, which was confirmed by the XDLVO theory. The related surface properties (Zeta potential, hydrodynamic diameter and hydrophobicity) at different ionic strength were determined and the interaction energy between Mt and GY2B were also calculated using the DLVO and XDLVO theories in KCl or CaCl2 solution. At low ionic strength (≤ 20 mM), GY2B adhesion onto Mt was primarily driven by long-range DLVO forces (e.g. electrostatic repulsion), while short-range (separation distance < 5 nm) Van der Waals and hydrophobic interactions played more important roles in the bacterial adhesion at higher ionic strength (50-100 mM). In addition, Mt had a better adhesion capacity to bacteria in Ca2+ solution than that in K+ solution, owing to less negative charge and lower energy barrier in mineral-bacteria system in Ca2+ solution. Overall, the adhesion of bacteria onto Mt could be evaluated well on the basis of the XDLVO theory along with thermodynamics analysis. This study provides valuable insights into the clay-mediated microbial remediation of hydrophobic organic contaminants in the environment.

Fast and efficient aqueous arsenic removal by functionalized MIL-100(Fe)/rGO/δ-MnO2 ternary composites: Adsorption performance and mechanism.

Because of its significant toxicological effects on the environment and human health, arsenic (As) is a major global issue. In this study, an Fe-based metal-organic framework (MOF) (Materials of Institut Lavoisier: MIL-100 (Fe)) which was impregnated with reduced graphene oxide (rGO) by using a simple hydrothermal method and coated with birnessite-type manganese oxide (δ-MnO2) using the one-pot reaction process (MIL-100(Fe)/rGO/δ-MnO2 nanocomposites) was synthesized and applied successfully in As removal. The removal efficiency was rapid, the equilibrium was achieved in 40 min and 120 min for As(III) and As(V), respectively, at a level of 5 mg/L. The maximum adsorption capacities of As(III) and As(V) at pH 2 were 192.67 mg/g and 162.07 mg/g, respectively. The adsorbent revealed high stability in pH range 2-9 and saturated adsorbent can be fully regenerated at least five runs. The adsorption process can be described by the pseudo-second-order kinetic model and Langmuir monolayer adsorption. The adsorption mechanisms consisted of electrostatic interaction, oxidation and inner sphere surface complexation.

Functional rGO aerogel as a potential adsorbent for removing hazardous hexavalent chromium: adsorption performance and mechanism.

A novel functional rGO aerogel was synthesized by a facile hydrothermal method. In this process, graphene oxide (GO) was used as the precursor and oxidant to synthesize the aerogels. Ethylenediaminetetraacetic acid disodium salt (EDTA-2Na) and pyrrole monomer (reducing agent) were selected to use as hole scavenger and nitrogen sources. The obtained EDTA-2Na/polypyrrole (Ppy)/rGO aerogel (EPGA) has a high adsorption capacity for Cr(VI) anions, and the maximum adsorption capacity reached 361 mg/g at 298 K at pH of 2. In addition, EPGA exhibited a good ability to selectively remove Cr(VI) anions under the effect of coexisting ions (Cl-, NO3-, SO42-, PO43-, Ni+, Cu2+, Zn2+, and Cd2+) and good regeneration ability. The kinetics process and adsorption isotherm can be fitted well with the pseudo-second-order kinetic model and Freundlich isotherm model, respectively. The removal mechanism involved electrostatic interaction, reduction, ion exchange, and chelation process. This work provides a simple and environmentally friendly synthetic route for EPGA, which will be a potential candidate for efficient removal Cr(VI) anions from industrial wastewater.

Synthesis of nano-scale zero-valent iron-reduced graphene oxide-silica nano-composites for the efficient removal of arsenic from aqueous solutions.

Design and synthesis of arsenic adsorbents with high performance and excellent stability has been still a significant challenge. In this study, we anchored nano-zero-valent iron (NZVI) on the surface of graphene-silica composites (GS) with high specific surface area, forming the NZVI/GS nano-composite. The prepared nano-materials were used to remove As(III) and As(V) through adsorption from aqueous solutions. The results indicated that NZVI particles were dispersed well on the surface of GS, and the NZVI/GS showed great potential to remove As(III) and As(V). Adsorption performance of NZVI/GS for As(III) and As(V) highly depended on the pH of solutions. The experimental data fitted well with the pseudo-second-order kinetic model and the Langmuir isotherm model. The calculated maximum adsorption capacities of NZVI/GS for As(III) and As(V) were up to 45.57 mg/g and 45.12 mg/g at 298 K, respectively, and the adsorption equilibrium could be reached within 60 min. The residual concentrations of As(III) and As(V) after treatment with 0.4 g/L NZVI/GS can meet with the drinking water standard of WHO when the initial concentrations were below 4 mg/L and 3 mg/L, respectively. Moreover, the as-prepared NZVI/GS had excellent anti-interference ability during the process of As removal in the presence of foreign ions. During the As removal process, As(III) was oxidized to As(V), which could be removed through adsorption by electrostatic attraction and complexation. These results indicated that the as-synthesized NZVI/GS composite is a promising adsorbent for the removal of arsenic from aqueous solutions.

Synthesis of graphene/SiO2@polypyrrole nanocomposites and their application for Cr(VI) removal in aqueous solution.

A novel hybrid nanocomposite, polypyrrole nanoparticles (PPy) anchored on the graphene/silica nanosheets with the high specific surface area (polypyrrole-graphene/silica, GS-PPy), was synthesized by a facile in situ polymerization and shows great potential to remove hexavalent chromium [Cr(VI)] in aqueous solutions. Characterizations by XRD, TEM, SEM, BET, FT-IR and XPS, have confirmed that the PPy nanoparticles were well-distributed on the surface of GS nanosheets. The effects of pH, contact time, the concentration of Cr(VI), temperature, coexisting ions and the number of adsorption-desorption cycles were studied. The maximum adsorption capacity of the GS-PPy for Cr(VI) was 429.2 mg g-1 at 298 K at pH 2, which was much higher than PPy nanoparticles and other related materials. The adsorption data fitted to the pseudo-second-order model and Langmuir isotherm model. The removal mechanism involved in electrostatic attraction, ion exchange and reduction process that partial adsorbed Cr(VI) was reduced to Cr(III). And Cr(III) was still retained on the surface of GS-PPy. The GS-PPy nanocomposite will be a potential candidate for the removal of Cr(VI) from the industrial waste water.

A novel modified graphene oxide/chitosan composite used as an adsorbent for Cr(VI) in aqueous solutions.

A novel adsorbent for removal of hexavalent chromium (Cr(VI)) from aqueous solutions has been successfully prepared by modifying graphene oxide/chitosan composite with disodium ethylenediaminetetraacetate (EDTA-2Na) (GEC). This modified composite was characterized by various technologies; including scanning electron microscopy (SEM), Transmission Electron Microscopy (TEM), X-ray diffraction (XRD) and Fourier transform infrared spectroscopy (FT-IR). Batch adsorption experiments were carried out to evaluate the adsorption of Cr(VI) by GEC under different conditions. The results indicate that the adsorption of Cr(VI) on GEC was highly pH-dependent, with the highest adsorption capacity (86.17mg/g) occurring at pH 2. The kinetics of adsorption exhibited pseudo-second-order behavior. The adsorption data were well described by the Freundlich isotherm model. The adsorption capacity increased with increasing temperature. The calculated thermodynamic parameters indicate that the adsorption is a spontaneous, endothermic and feasible process. The further regeneration experiments showed the adsorption capacity of GEC for Cr(VI) decreased 5% after 7 times reuse, indicating the potential of the as-prepared material for practical application.

Distribution, sources, and fluxes of heavy metals in the Pearl River Delta, South China.

Riverine samples were collected at various locations in the Pearl River Delta (PRD) to determine the concentrations of heavy metals (Cr, Ni, Cu, Mn, Zn, Cd, and Pb) in time and space and to estimate the fluxes of heavy metals to the coastal waters off South China. Most of the elements exhibit clear temporal and spatial trends. Principal component analysis shows that surface erosion is the major factor affecting metal concentrations in particulates in the PRD. Natural geology is an important source of these heavy metals. The annual fluxes of Cr, Ni, Cu, Mn, Zn, Cd, and Pb in upstream and downstream were 445, 256, 241, 3293, 1279, 12, and 317 t/year and 1823, 1144, 1786, 15,634, 6183, 74, and 2017 t/year, respectively. A comparison indicated that the annual fluxes of Mn accounted for 1.3% of the global river fluxes, whereas other elements contribute <1%.

Pd nanoparticles supported on MIL-101/reduced graphene oxide photocatalyst: an efficient and recyclable photocatalyst for triphenylmethane dye degradation.

To improve the photocatalytic efficiency of chromium-based metal-organic framework (MIL-101) photocatalyst, Pd nanoparticles and reduced graphene oxide were used to modify the MIL-101 via a facile method. The resulting novel photocatalyst was characterized by UV-vis diffuse reflectance spectra (DRS), powder X-ray diffraction (XRD), transmission electron microscopy (TEM), and X-ray photoelectron spectroscopy (XPS). It was indicated that the photocatalyst afforded high photocatalytic efficiency for degradation of two triphenylmethane dyes, brilliant green and acid fuchsin, under exposure to visible light irradiation. Cyclic experiments demonstrated that the photocatalyst showed good reusability and stability for the dye degradation.

Fast adsorption of nickel ions by porous graphene oxide/sawdust composite and reuse for phenol degradation from aqueous solutions.

This work describes the preparation of an effective and low-cost porous graphene oxide/sawdust composite by a freeze-drying method. The composite exhibits a strong ability to adsorb nickel ions. The nickel ions adsorbed on graphene oxide/sawdust composite was reduced by sodium borohydride to generate a catalyst which was used in the degradation of phenol in water. The composite and the catalyst were characterized by XPS, FTIR, XRD and SEM. The adsorption of nickel ions by graphene oxide/sawdust composite was initially very fast and then slowly reached equilibrium in around 30 min. The adsorption of nickel ions by the composite could be well-described by the Freundlich isotherm model and the pseudo-second order kinetic model. The performance of the catalyst in phenol degradation was studied as a function of reaction time, dosage, temperature and initial pH. It was found that the catalyst optimally improved the degradation rate at pH 10 with a dose of 2 g/L in about 30 min. The results show that the degradation of phenol was an endothermic reaction and was a good fit to the Langmuir isotherm model.

Removal of para-nitrochlorobenzene from aqueous solution on surfactant-modified nanoscale zero-valent iron/graphene nanocomposites.

This study demonstrated a remarkably simple and efficient method for the synthesis of nanoscale zero-valent iron (NZVI)/graphene (GN) nanocomposites. In order to prevent the agglomeration and restack of nanocomposites, chemical functionalization of nanocomposites with cetyltrimethylammonium bromide was proposed. The adsorption performance of surfactant-modified NZVI/GN nanocomposites was evaluated for the removal of para-nitrochlorobenzene (p-NCB) from aqueous solutions. The characteristics of nanocomposites were characterized by X-ray diffraction, BET surface area, Fourier transform infrared spectrum, thermogravimetric analysis and scanning electron microscopy. The effect factors including initial solution pH, contact time, reaction temperature, dosage, initial concentration of humic acid (HA) on the adsorption property of p-NCB onto surfactant-modified nanocomposites were investigated. The adsorption kinetics fitted well with pseudo-second-order model. The adsorption capacity of p-NCB on surfactant-modified nanocomposites inferred from the Langmuir model was 105.15 mg/g at 293 K. The thermodynamic parameters indicated that the adsorption of p-NCB onto surfactant-modified nanocomposites was an exothermic and spontaneous process. HA had a strong suppression effect on p-NCB uptake in the adsorption experiment.