Gaosheng Zhang

Removal of phosphate from water by a Fe-Mn binary oxide adsorbent

Phosphate removal is important in the control of eutrophication of water bodies and adsorption is one of the promising approaches for this purpose. A Fe-Mn binary oxide adsorbent with a Fe/Mn molar ratio of 6:1 for phosphate removal was synthesized by a simultaneous oxidation and coprecipitation process. Laboratory experiments were carried out to investigate adsorption kinetics and equilibrium, in batch mode. The effects of different experimental parameters, namely contact time, initial phosphate concentration, solution pH, and ionic strength on the phosphate adsorption were investigated. The adsorption data were analyzed by both Freundlich and Langmuir isotherm models and the data were well fit by the Freundlich isotherm model. Kinetic data correlated well with the pseudo-second-order kinetic model, suggesting that the adsorption process might be chemical sorption. The maximal adsorption capacity was 36 mg/g at pH 5.6. The phosphate adsorption was highly pH dependent. The effects of anions such as Cl(-),SO42-, and CO32- on phosphate removal were also investigated. The results suggest that the presence of these ions had no significant effect on phosphate removal. The phosphate removal was mainly achieved by the replacement of surface hydroxyl groups by the phosphate species and formation of inner-sphere surface complexes at the water/oxide interface. In addition, the adsorbed phosphate ions can be effectively desorbed by dilute NaOH solutions. This adsorbent, with large adsorption capacity and high selectivity, is therefore a very promising adsorbent for the removal of phosphate ions from aqueous solutions.

Nanostructured iron(III)-copper(II) binary oxide: A novel adsorbent for enhanced arsenic removal from aqueous solutions

To obtain a highly efficient and low-cost adsorbent for arsenic removal from water, a novel nanostructured Fe-Cu binary oxide was synthesized via a facile co-precipitation method. Various techniques including BET surface area measurement, powder XRD, SEM, and XPS were used to characterize the synthetic Fe-Cu binary oxide. It showed that the oxide was poorly crystalline, 2-line ferrihydrite-like and was aggregated with many nanosized particles. Laboratory experiments were performed to investigate adsorption kinetics, adsorption isotherms, pH adsorption edge and regeneration of spent adsorbent. The results indicated that the Fe-Cu binary oxide with a Cu: Fe molar ratio of 1:2 had excellent performance in removing both As(V) and As(III) from water, and the maximal adsorption capacities for As(V) and As(III) were 82.7 and 122.3 mg/g at pH 7.0, respectively. The values are favorable, compared to those reported in the literature using other adsorbents. The coexisting sulfate and carbonate had no significant effect on arsenic removal. However, the presence of phosphate obviously inhibited the arsenic removal, especially at high concentrations. Moreover, the Fe-Cu binary oxide could be readily regenerated using NaOH solution and be repeatedly used. The Fe-Cu binary oxide could be a promising adsorbent for both As(V) and As(III) removal because of its excellent performance, facile and low-cost synthesis process, and easy regeneration.

Adsorptive removal of arsenic from water by an iron-zirconium binary oxide adsorbent.

Arsenate and arsenite may exist simultaneously in groundwater and have led to a greater risk to human health. In this study, an iron-zirconium (Fe-Zr) binary oxide adsorbent for both arsenate and arsenite removal was prepared by a coprecipitation method. The adsorbent was amorphous with a specific surface area of 339 m(2)/g. It was effective for both As(V) and As(III) removal; the maximum adsorption capacities were 46.1 and 120.0 mg/g at pH 7.0, respectively, much higher than for many reported adsorbents. Both As(V) and As(III) adsorption occurred rapidly and achieved equilibrium within 25 h, which were well fitted by the pseudo-second-order equation. Competitive anions hindered the sorption according to the sequence PO(4)(3-)>SiO(3)(2-)>CO(3)(2-)>SO(4)(2-). The ionic strength effect experiment, measurement of zeta potential, and FTIR study indicate that As(V) forms inner-sphere surface complexes, while As(III) forms both inner- and outer-sphere surface complexes at the water/Fe-Zr binary oxide interface. The high uptake capability and good stability of the Fe-Zr binary oxide make it a potentially attractive adsorbent for the removal of both As(V) and As(III) from water.

Adsorption behavior and mechanism of arsenate at Fe–Mn binary oxide/water interface

Preliminary study revealed that a prepared Fe-Mn binary oxide adsorbent with a Fe:Mn molar ratio of 3:1 was more effective for As(V) removal than pure amorphous FeOOH, which was unanticipated. In this paper, the As(V) adsorption capacities of Fe-Mn binary oxide and amorphous FeOOH were compared in detail. Furthermore, the adsorption behaviors as well as adsorption mechanism of As(V) at the Fe-Mn binary oxide/water interface were investigated. The higher uptake of As(V) by the Fe-Mn binary oxide may be due to its higher surface area (265 m(2)/g) and pore volume (0.47 cm(3)/g) than those of amorphous FeOOH. The As(V) adsorption process on the Fe-Mn binary oxide is endothermic and the increase of temperature is favoring its adsorption. A slight increase in the As(V) adsorption was observed with increasing ionic strength of the solution, which indicated that As(V) anions might form inner-sphere surface complexes at the oxide/water interface. The Zeta potential along with FTIR analysis confirmed further the formation of inner-sphere surface complexes between As(V) anions and the surface of Fe-Mn binary oxide. In addition, the influences of coexisting ions such as phosphate, bicarbonate, silicate, sulfate, chloride, calcium and magnesium which are generally present in groundwater on As(V) adsorption were examined. Among the tested anions, chloride and sulfate had no significant effect on As(V) removal, silicate decreased obviously the As(V) removal, while phosphate caused the greatest percentage decrease in As(V) adsorption. On the contrary, the presence of cations of Ca(2+) and Mg(2+) enhanced the adsorption of As(V).

Respective Role of Fe and Mn Oxide Contents for Arsenic Sorption in Iron and Manganese Binary Oxide: An X-ray Absorption Spectroscopy Investigation

In our previous studies, a synthesized Fe-Mn binary oxide was found to be very effective for both As(V) and As(III) removal in aqueous phase, because As(III) could be easily oxidized to As(V). As(III) oxidation and As(V) sorption by the Fe-Mn binary oxide may also play an important role in the natural cycling of As, because of its common occurrence in the environment. In the present study, the respective role of Fe and Mn contents present in the Fe-Mn binary oxide on As(III) removal was investigated via a direct in situ determination of arsenic speciation using X-ray absorption spectroscopy. X-ray absorption near edge structure results indicate that Mn atoms exist in a mixed valence state of +3 and +4 and further confirm that MnOx (1.5 < x < 2) content is mainly responsible for oxidizing As(III) to As(V) through a two-step pathway [reduction of Mn(IV) to Mn(III) and subsequent Mn(III) to Mn(II)] and FeOOH content is dominant for adsorbing the formed As(V). No significant As(III) oxidation by pure FeOOH had been observed during its sorption, when the system was exposed to air. The extended X-ray absorption fine structure results reveal that the As surface complex on both the As(V)- and As(III)-treated sample surfaces is an inner-sphere bidentate binuclear corner-sharing complex with an As-M (M = Fe or Mn) interatomic distance of 3.22-3.24 Å. In addition, the MnOx and FeOOH contents exist only as a mixture, and no solid solution is formed. Because of its high effectiveness, low cost, and environmental friendliness, the Fe-Mn binary oxide would play a beneficial role as both an efficient oxidant of As(III) and a sorbent for As(V) in drinking water treatment and environmental remediation.

Arsenate uptake and arsenite simultaneous sorption and oxidation by Fe-Mn binary oxides: Influence of Mn/Fe ratio, pH, Ca2+, and humic acid

Arsenate retention, arsenite sorption and oxidation on the surfaces of Fe-Mn binary oxides may play an important role in the mobilization and transformation of arsenic, due to the common occurrence of these oxides in the environment. However, no sufficient information on the sorption behaviors of arsenic on Fe-Mn binary oxides is available. This study investigated the influences of Mn/Fe molar ratio, solution pH, coexisting calcium ions, and humic acids have on arsenic sorption by Fe-Mn binary oxides. To create Fe-Mn binary oxides, simultaneous oxidation and co-precipitation methods were employed. The Fe-Mn binary oxides exhibited a porous crystalline structure similar to 2-line ferrihydrite at Mn/Fe ratios 1:3 and below, whereas exhibited similar structures to δ-MnO(2) at higher ratios. The As(V) sorption maximum was observed at a Mn/Fe ratio of 1:6, but As(III) uptake maximum was at Mn/Fe ratio 1:3. However, As(III) adsorption capacity was much higher than that of As(V) at each Mn/Fe ratio. As(V) sorption was found to decrease with increasing pH, while As(III) sorption edge was different, depending on the content of MnO(2) in the binary oxides. The presence of Ca(2+) enhanced the As(V) uptake under alkaline pH, but did not significantly influence the As(III) sorption by 1:9 Fe-Mn binary oxide; whereas the presence of humic acid slightly reduced both As(V) and As(III) uptake. These results indicate that As(III) is more easily immobilized than As(V) in the environment, where Fe-Mn binary oxides are available as sorbents and they represent attractive adsorbents for both As(V) and As(III) removal from water and groundwater.

Efficient removal of arsenic from water using a granular adsorbent: Fe–Mn binary oxide impregnated chitosan bead

A novel sorbent of Fe-Mn binary oxide impregnated chitosan bead (FMCB) was fabricated through impregnating Fe-Mn binary oxide into chitosan matrix. The FMCB is sphere-like with a diameter of 1.6-1.8 mm, which is effective for both As(V) and As(III) sorption. The maximal sorption capacities are 39.1 and 54.2 mg/g, respectively, outperforming most of reported granular sorbents. The arsenic was mainly removed by adsorbing onto the Fe-Mn oxide component. The coexisting SO4(2-), HCO3(-) and SiO3(2-) have no great influence on arsenic sorption, whereas, the HPO4(2-) shows negative effects. The arsenic-loaded FMCB could be effectively regenerated using NaOH solution and repeatedly used. In column tests, about 1500 and 3200 bed volumes of simulated groundwater containing 233 μg/L As(V) and As(III) were respectively treated before breakthrough. These results demonstrate the superiority of the FMCB in removing As(V) and As(III), indicating that it is a promising candidate for arsenic removal from real drinking water.

Evidence for the Stepwise Behavioral Response Model (SBRM): The effects of Carbamate Pesticides on medaka (Oryzias latipes) in an online monitoring system

The Stepwise Behavioral Response Model (SBRM), which is a conceptual model, postulated that an organism displays a time-dependent sequence of compensatory Stepwise Behavioral Response (SBR) during exposure to pollutants above their respective thresholds of resistance. In order to prove the model, in this study, the behavioral responses (BRs) of medaka (Oryzias latipes) in the exposure of Arprocarb (A), Carbofuran (C) and Methomyl (M) were analyzed in an online monitoring system (OMS). The Self-Organizing Map (SOM) was utilized for patterning the obtained behavioral data in 0.1 TU (Toxic Unit), 1 TU, 2 TU, 5 TU, 10 TU and 20 TU treatments with control. Some differences among different Carbamate Pesticides (CPs) were observed in different concentrations and the profiles of behavior strength (BS) on SOM were variable depending upon levels of concentration. The time of the first significant decrease of BS (SD-BS) was in inverse ratio to the CP concentrations. Movement behavior showed by medaka mainly included No effect, Stimulation, Acclimation, Adjustment (Readjustment) and Toxic effect, which proved SBRM as a time-dependence model based on the time series BS data. Meanwhile, it was found that SBRM showed evident stress-dependence. Therefore, it was concluded that medaka SBR was both stress-dependent and time-dependent, which supported and developed SBRM, and data mining by SOM could be efficiently used to illustrate the behavioral processes and to monitor toxic chemicals in the environment.

Simultaneous removal of arsenate and arsenite by a nanostructured zirconium-manganese binary hydrous oxide: Behavior and mechanism

Arsenate and arsenite typically co-exist in groundwater. Arsenite is more toxic than arsenate, while it is more difficult to be removed than arsenate. In order to effectively remove arsenate and arsenite simultaneously from water solution, a nanostructured zirconium-manganese binary hydrous oxide was successfully developed in this study. The amorphous sorbent was aggregate of nanoparticles with a high surface area of 213 m(2)g(-1). Our sorption experiments showed that the nano-scale particles could effectively oxidize As(III) to As(V) and greatly remove both As(V) and As(III). The maximal adsorption capacities of As(V) and As(III) were 80 and 104 mg g(-1) at pH 5.0, respectively. As(V) uptake may be mainly achieved through replacement of hydroxyl groups and sulfate anions on the surface of the oxide and formation of inner complexes. The As(III) removal was essentially due to a sorption coupled with oxidation process; the MnO2 was mainly responsible for oxidization of As(III) to As(V) that was subsequently adsorbed onto ZrO2.

A new online monitoring and management system for accidental pollution events developed for the regional water basin in Ningbo, China

Due to urgency of the accidental pollution events (APE) on one side and the variability in water quality data on the other side, a new online monitoring and management system (OMMS) was developed for the purpose of sustainable water quality management and human health protection as well. The Biological Early Warning System (BEWS) based on the behavioral responses (behavior strength) of medaka (Oryzias latipes) were built in combination with the physico-chemical factor monitoring system (PFMS) in OMMS. OMMS included a monitoring center and six monitoring stations. Communication between the center and the peripheral stations was conducted by the General Packet Radio Service (GPRS) network transmission complemented by a dial-up connection for use when GPRS was unavailable. OMMS could monitor water quality continuously for at least 30 days. Once APEs occurred, OMMS would promptly notify the administrator to make some follow up decisions based on the Emergency Treatment of APE. Meanwhile, complex behavioral data were analyzed by Self-Organizing Map to properly classify behavior response data before and after contamination. By utilizing BEWS, PFMS and the modern data transmission in combination, OMMS was efficient in monitoring the water quality more realistically.