The sorption of selenite (SeO32−) and selenate (SeO42−) onto Fe3O4 nanomaterials produced by non microwave-assisted or microwave-assisted synthetic techniques was investigated through use of the batch technique. The phase of both synthetic nanomaterials was determined to be magnetite by X-ray diffraction. The average grain sizes of non microwave-assisted and microwave-assisted synthetic Fe3O4 were determined to be 27 and 25 nm, respectively through use of the Scherrer's equation. Sorption of selenite was pH independent in the pH range of 2-6, while sorption of selenate decreased at pH 5 and 6. The addition of Cl− had no significant effect on selenite or selenate binding, while the addition of NO3− only affected selenate binding to the microwave assisted Fe3O4. A decrease of selenate binding to both synthetic particles was observed after the addition of SO42− while selenite binding was not affected. The addition of PO43− beginning at concentrations of 0.1 ppm had the most prominent effect on the binding of both selenite and selenate. The capacities of binding, determined through the use of Langmuir isotherm, were found to be 1923 and 1428 mg Se/kg of non microwave-assisted Fe3O4 and 2380 and 2369 mg Se/kg of microwave-assisted Fe3O4 for selenite and selenate, respectively.
The binding of Cr(III) and Cr(VI) to synthetic nano-magnetie particles synthesized under open vessel conditions and a microwave assisted hydrothermal synthesis techniques was investigated. Batch studies showed that the binding of both the Cr(III) and Cr(VI) bound to the nano-materials in a pH dependent manner. The Cr(III) maximized at binding at pH 4 and 100% binding. Similarly, the Cr(VI) ions showed a maximum binding of 100% at pH 4. The data from the time dependency studies showed for the most part the majority of the binding occurred within the first 5 minutes of contact with the nanomaterial and remained constant thereafter. In addition, the effects of the possible interferences were investigated which showed some effects on the binding of both Cr(III) and Cr(VI). However, the interferences never completely eliminated the chromium binding. Isotherm studies conducted at room temperature showed the microwave synthesized nanomaterials had a binding capacity of 1208 ± 43.9 mg/g and 555 ± 10.5 mg/g for Cr(VI) and Cr(III), respectively. However, the microwave assisted synthesized nanomaterials had capacities of 1705 ± 14.5 and 555± 10.5 mg/g for Cr(VI) and Cr(III), respectively. XANES studies showed the Cr(VI) was reduced to Cr(III), and the Cr(III) remained as Cr(III). In addition, the XANES studies indicated that the chromium remained coordinated in an octahedral arrangement of oxygen atoms.
& This study investigated the effects of pH, reaction time, competitive anions, and adsorption capacity through the use of Langmuir isotherms of selenite and selenate binding to engineered Mn 3 O 4 nanomaterials aged using two different techniques through use of dynamic reaction cell inductively coupled plasma-mass spectrometry (DRC-ICP-MS). The phases and average grain sizes of the synthesized materials were determined through x-ray diffraction and Scherrer's equation. The optimal binding occurred at pH 4 within 10 min of contact time for both materials. The addition of Cl À , NO À 3 ; SO 2À 4 , and PO 3À 4 all decreased selenate binding, while only SO 2À 4 and PO 3À 4 decreased selenite binding. The binding capacities were found to be 507 and 800 mg Se=kg of non-microwave-assisted Mn 3 O 4 for selenite and selenate, respectively. The microwave-assisted Mn 3 O 4 displayed binding capacities of 1000 and 934.5 mg Se=kg of nanomaterial for selenite and selenate, respectively.
Increasing concentrations of selenium oxoanions in the environment are placing many animals at risk for reproduction failure and deformities. The understanding of binding mechanisms of selenium oxoanions to iron and manganese based oxide minerals could lead to enhanced understanding of selenium mobility in the environment. In this study, the binding mechanisms of selenium oxoanions, selenite and selenate, to non microwave-assisted and microwave-assisted synthetic Fe3O4, Mn3O4, and MnFe2O4 nanomaterials were investigated through the use of X-ray absorption spectroscopy. The X-ray absorption near-edge structure (XANES) spectroscopy studies revealed the oxidation state of selenite and selenate remains the same after binding occurs to all nanomaterials in pH 2, 4, or 6 environments. The binding modes of selenite and selenate were determined to be bidentate binuclear through use of Extended x-ray absorption fine structure (EXAFS) and were independent of nanomaterials, synthetic technique, and pH.
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