Graphene oxide and chitosan microspheres modified with α–FeO(OH) (α–FeO(OH)/GOCS) are prepared and utilized to investigate the performance and mechanism for Cr(VI) removal from aqueous solutions and the possibility of Fe secondary pollution. Batch experiments were carried out to identify the effects of pH, mass, and volume ratio (m/v), coexisting ions, time (t), temperature (T), and Cr(VI) initial concentration (C0) on Cr(VI) removal, and to evaluate adsorption kinetics, equilibrium isotherm, and thermodynamics, as well as the possibility of Fe secondary pollution. The results showed that Cr(VI) adsorption increased with C0, t, and T but decreased with increasing pH and m/v. Coexisting ions inhibited Cr(VI) adsorption, and this inhibition increased with increasing concentration. The influence degrees of anions and cations on the Cr(VI) adsorption in descending order were SO42− > PO42− > NO3− > Cl− and Ca2+ > Mg2+ > Mn2+, respectively. The equilibrium adsorption capacity of Cr(VI) was the highest at 24.16 mg/g, and the removal rate was 97.69% under pH = 3, m/v = 1.0 g/L, T = 298.15 K, and C0 = 25 mg/L. Cr(VI) adsorption was well fitted to a pseudo-second-order kinetic model and was spontaneous and endothermic. The best fit of Cr(VI) adsorption with the Langmuir and Sips models indicated that it was a monolayer and heterogeneous adsorption. The fitted maximum adsorption capacity was 63.19 mg/g using the Sips model under 308.15 K. Cr(VI) removal mainly included electrostatic attraction between Cr(VI) oxyanions with surface Fe–OH2+, and the adsorbed Cr(VI) was partially reduced to Cr(III) and then precipitated on the surface. In addition, there was no Fe secondary pollution during Cr(VI) adsorption.
A magnetite graphene oxide chitosan (MGOCS) composite microsphere was specifically prepared to efficiently adsorb As(III) from aqueous solutions. The characterization analysis of BET, XRD, VSM, TG, FTIR, XPS, and SEM-EDS was used to identify the characteristics and adsorption mechanism. Batch experiments were carried out to determine the effects of the operational parameters and to evaluate the adsorption kinetic and equilibrium isotherm. The results show that the MGOCS composite microsphere with a particle size of about 1.5 mm can be prepared by a straightforward method of dropping FeCl2, graphene oxide (GO), and chitosan (CS) mixtures into NaOH solutions and then drying the mixed solutions at 45 °C. The produced MGOCS had a strong thermal stability with a mass loss of <30% below 620 °C. The specific surface area and saturation magnetization of the produced MGOCS was 66.85 m2/g and 24.35 emu/g, respectively. The As(III) adsorption capacity (Qe) and removal efficiency (Re) was only 0.25 mg/g and 5.81% for GOCS, respectively. After 0.08 mol of Fe3O4 modification, more than 53% of As(III) was efficiently removed by the formed MGOCS from aqueous solutions over a wide pH range of 5–10, and this was almost unaffected by temperature. The coexisting ion of PO43− decreased Qe from 3.81 mg/g to 1.32 mg/g, but Mn2+ increased Qe from 3.50 mg/g to 4.19 mg/g. The As(III) adsorption fitted the best to the pseudo-second-order kinetic model, and the maximum Qe was 20.72 mg/g as fitted by the Sips model. After four times regeneration, the Re value of As(III) slightly decreased from 76.2% to 73.8%, and no secondary pollution of Fe happened. Chemisorption is the major mechanism for As(III) adsorption, and As(III) was adsorbed on the surface and interior of the MGOCS, while the adsorbed As(III) was partially oxidized to As(V) accompanied by the reduction of Fe(III) to Fe(II). The produced As(V) was further adsorbed through ligand exchange (by forming Fe–O–As complexes) and electrostatic attraction, enhancing the As(III) removal. As an easily prepared and environmental-friendly composite, MGOCS not only greatly adsorbs As(III) but also effectively removes Cr(VI) and As(V) (Re > 60%) and other metals, showing a great advantage in the treatment of heavy metal-contaminated water.
Mineral extraction can significantly affect the groundwater flow and hydrochemical environment. However, for hilly areas, significant ground elevation changes and complex geological conditions make it difficult to accurately analyze and predict the impact of mineral mining. This study takes the Nuodong rare earth mining area as an example. Based on field investigations and experiments, GOCAD software (version 2022) was used to establish a geological model in combination with GMS numerical simulation software, which was used to build a groundwater flow model and a solute transport model. The flow model in the hilly area indicated that the absolute error between the simulated and measured water levels of each observation well is 0.554 m. The solute-transport model showed that the maximum pollutant concentration of ammonia-nitrogen (NH3-N) in the liquid injection area, stream area, and village area monitoring wells reaches 139.15, 27.9, and <0.5 mg/L, respectively. During the mining period, streams in the area are affected by NH3-N, which threatens the safety of the water for mine area residents. To control pollutant transport, two stages of pumping were adopted to reduce NH3-N concentrations in groundwater. After adopting the first stage, the peak concentration of the stream area monitoring wells decreased significantly, with the maximum peak concentration decreasing from 27.9 mg/L to 5.51 mg/L. Based on the results of the first stage of the pump-out treatment, a second stage was adopted. The model results showed that the peak concentration of NH3-N pollutants discharged into the stream is less than 0.5 mg/L. The results provide a theoretical basis and reference for groundwater monitoring and pollution control after mining in this area.
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