In this study, a manganese oxide, Mn3O4 was used to remove chromium(III) and chromium(VI) from aqueous solutions. The Mn3O4 nanomaterial was synthesized through a precipitation method, and was characterized using XRD, which confirmed the material had a crystal structure similar to hausmannite. In addition, using Scherrer’s equation it was determined that the nanomaterial had an average grain size of 19.5 ± 1.10 nm. A study of the effects of pH on the binding of chromium(III) and chromium(VI) showed that the optimum binding pH was 4 and 3 respectively. Batch isotherm studies were performed to determine the binding capacity of chromium(III), which was determined to be 18.7 mg/g, 41.7 mg/g, and 54.4 mg/g respectively for 4°C, 21°C, and 45°C. Chromium(VI) on the other hand had lower binding capacities of 2.5 mg/g, 4.3 mg/g, and 5.8 mg/g for 4°C, 21°C, 45°C, respectively. Thermodynamic studies performed indicated the sorption process was for the most part controlled by physisorption. The ΔG for the sorption of chromium(III) and Chromium(VI) ranged from −0.9 to −13 kJ/mol, indicating a spontaneous reaction was occurring. The enthalpy indicated a endothermic reaction was occurring during the binding and show ΔH values of 70.6 and 19.1 kJ.mol for chromium(III) and Chromium(VI), respectively. In addition, ΔS for the reaction had positive values of 267 and 73 J/mol for chromium(III) and chromium(VI) which indicate a spontaneous reaction. In addition, the sorption process was found to follow pseudo second order kinetic and the activation energy studies indicated the binding process occurred through chemisorption.
Wastewater compounds are frequently detected in urban shallow groundwater. Sources include sewage or reclaimed wastewater, but origins are often unknown. In a prior study, wastewater compounds were quantified in waters sampled from shallow groundwater wells in a small coastal California city. Here, we resampled those wells and expanded sample analyses to include sewage- or reclaimed water-specific indicators, i.e. pharmaceutical and personal care product chemicals or disinfection byproducts. Also, we developed a geographic information system (GIS)-based model of sanitary sewer exfiltration probability--combining a published pipe failure model accounting for sewer pipe size, age, materials of construction, with interpolated depths to groundwater--to determine if sewer system attributes relate to wastewater compounds in urban shallow groundwater. Across the wells, groundwater samples contained varying wastewater compounds, including acesulfame, sucralose, bisphenol A, 4-tert-octylphenol, estrone and perfluorobutanesulfonic acid (PFBS). Fecal indicator bacterial concentrations and toxicological bioactivities were less than known benchmarks. However, the reclaimed water in this study was positive for all bioactivity tested. Excluding one well intruded by seawater, the similarity of groundwater to sewage, based on multiple indicators, increased with increasing sanitary sewer exfiltration probability (modeled from infrastructure within ca. 300 m of each well). In the absence of direct exfiltration or defect measurements, sewer exfiltration probabilities modeled from the collection system's physical data can indicate potential locations where urban shallow groundwater is contaminated by sewage.
Micronutrient deficiencies in global food chains are a significant cause of ill health around the world, particularly in developing countries. Agriculture is the primary source of nutrients required for sound health, and as the population has continued to grow, the agricultural sector has come under pressure to improve crop production, in terms of both quantity and quality, to meet the global demands for food security. The use of engineered nanomaterial (ENM) has emerged as a promising technology to sustainably improve the efficiency of current agricultural practices as well as overall crop productivity. One promising approach that has begun to receive attention is to use ENM as seed treatments to biofortify agricultural crop production and quality. This review highlights the current state of the science for this approach as well as critical knowledge gaps and research needs that must be overcome to optimize the sustainable application of nano-enabled seed fortification approaches.
The effect of surface or lattice modification of nanoparticles (NPs) on terrestrial plants is poorly understood. We investigated the impact of different zinc oxide (ZnO) NPs on green pea (Pisum sativum L.), one of the highest consumed legumes globally. Pea plants were grown for 65 d in soil amended with commercially available bare ZnO NPs (10 nm), 2 wt% alumina doped (Al2O3@ZnO NPs, 15 nm), or 1 wt% aminopropyltriethoxysilane coated NPs (KH550@ZnO NP, 20 nm) at 250 and 1000 mg NP/kg soil inside a greenhouse. Bulk (ZnO) and ionic Zn (zinc chloride) were included as controls. Plant fresh and dry biomass, changes in leaf pigment concentrations, elements (Zn, Al, Si), and protein and carbohydrate profile of green pees were quantified upon harvest at 65 days. With the exception of the coated 1000 mg/kg NP treatment, fresh and dry weight were unaffected by Zn exposure. Although, all treated plants showed higher tissue Zn than controls, those exposed to Al2O3@ZnO NPs at 1000 mg/kg had greater Zn concentration in roots and seeds, compared to bulk Zn and the other NP treatments, keeping Al and Si uptake largely unaffected. Higher Zn accumulation in green pea seeds were resulted in coated ZnO at 250 mg/kg treatments. In leaves, Al2O3@ZnO NP at 250 mg/kg significantly increased Chl-a and carotenoid concentrations relative to the bulk, ionic, and the other NP treatments. The protein and carbohydrate profiles remained largely unaltered across all treatments with the exception of Al2O3@ZnO NPs at 1000 mg/kg where sucrose concentration of green peas increased significantly, which is likely a biomarker of stress. Importantly, these findings demonstrate that lattice and surface modification can significantly alter the fate and phytotoxic effects of ZnO NPs in food crops and seed nutritional quality. To the authors' knowledge, this is the first report of a life cycle study on comparative toxicity of bare, coated, and doped ZnO NPs on a soil-grown food crop.
Nano-sized Fe3O4 and Fe2O3 were synthesized using a precipitation method. The nanomaterials were tested as adsorbents for the removal of both Cu2+ and Pb2+ ions. The nanomaterials were characterized using X-ray powder diffraction to determine both the phase and the average grain size of the synthesized nanomaterials. Batch pH studies were performed to determine the optimum binding pH for both the Cu2+ and Pb2+ to the synthesized nanomaterials. The optimum binding was observed to occur at pH 4 and above. Time dependency studies for Cu2+ and Pb2+ showed the binding occurred within the first five minutes of contact and remained constant up to 2 hours of contact. Isotherm studies were utilized to determine the binding capacity of each of the nanomaterials for Cu2+ and Pb2+. The binding capacity of Fe3O4 with Cu2+ and Pb2+ were 37.04 mg/g and 166.67 mg/g, respectively. The binding capacities of the Fe2O3 nanomaterials with Cu2+ and Pb2+ were determined to be 19.61 mg/g and 47.62 mg/g, respectively. In addition, interference studies showed no significant reduction in the binding of either Cu2+ or Pb2+ to the Fe3O4 or Fe2O3 nanomaterials in the presence of solutions containing the individual ions Na+, K+, Mg2+ and Ca2+ or a solution consisting of a combination of all the aforementioned cations in one solution.
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