Search for: All records

The unique properties of the lanthanide (Ln) elements make them critical components of modern technologies, such as lasers, anti-corrosive films and catalysts. Thus, there is significant interest in establishing structure–property relationships for Ln-containing materials to advance these technologies. Extended X-ray absorption fine structure (EXAFS) is an excellent technique for this task considering its ability to determine the average local structure around the Ln atoms for both crystalline and amorphous materials. However, the limited availability of EXAFS reference spectra of the Ln oxides and challenges in the EXAFS analysis have hindered the application of this technique to these elements. The challenges include the limitedk-range available for the analysis due to the superposition ofL-edges on the EXAFS, multielectron excitations (MEEs) creating erroneous peaks in the EXAFS and the presence of inequivalent absorption sites. Herein, we removed MEEs to model the local atomic environment more accurately for light Ln oxides. Further, we investigated the use of cubic and non-cubic lattice expansion to minimize the fitting parameters needed and connect the fitting parameters to physically meaningful crystal parameters. The cubic expansion reduced the number of fitting parameters but resulted in a statistically worse fit. The non-cubic expansion resulted in a similar quality fit and showed non-isotropic expansion in the crystal lattice of Nd₂O₃. In total, the EXAFS spectra and the fits for the entire set of Ln oxides (excluding promethium) are included. The knowledge developed here can assist in the structural determination of a wide variety of Ln compounds and can further studies on their structure–property relationships. 

Abstract Struvite (MgNH₄PO₄·6H₂O) has been precipitated from liquid waste streams to recover valuable nutrients, such as phosphorus (P) and nitrogen (N), that can be used as an alternative fertilizer‐P source. Because prior research has focused on greenhouse studies, it is necessary to expand struvite evaluations to the field‐scale to include row‐crop responses. The objective of this field study was to evaluate the effects of two struvite materials (electrochemically precipitated struvite, ECST; and chemically precipitated struvite, CPST) relative to other common fertilizer‐P sources (diammonium phosphate, DAP; triple superphosphate, TSP; rock phosphate, RP; and monoammonium phosphate, MAP) on soybean [Glycine max(L.) Merr.] response and economics in two consecutive growing seasons in a P‐deficient, silt‐loam soil (Aquic Fraglossudalfs) in eastern Arkansas. Averaged across years, soybean aboveground tissue P uptake was largest (P < .05) from ECST (28.4 kg ha⁻¹), which was similar to CPST (26.7 kg ha⁻¹) and TSP (25.9 kg ha⁻¹) and was smallest from RP (21.4 kg ha⁻¹). In 2019, seed yield was largest (P < .05) from ECST (4.1 Mg ha⁻¹), which was similar to DAP, CPST, RP, TSP, and MAP, and was smallest from the unamended control (3.6 Mg ha⁻¹). In 2020, seed yield was numerically greatest from CPST (2.8 Mg ha⁻¹) and was numerically smallest from ECST (2.2 Mg ha⁻¹). Results showed that wastewater‐recovered struvite materials have the potential to be a viable, alternative fertilizer‐P source for soybean production in a P‐deficient, silt‐loam soil, but further work is needed to confirm struvite's cost effectiveness. 

The perception of wastewater as a resource rather than a pollutant has not been well emphasized. Phosphorus (P) can be precipitated from wastewaters as the mineral struvite (MgNH4PO4·6H2O), which can be a potential sustainable alternative to the limited, rock phosphate (RP)-dependent, traditional fertilizer-P sources for agricultural production. This field study evaluated the effects of electrochemically precipitated struvite (ECST) and chemically precipitated struvite (CPST) compared to other conventional fertilizer-P materials [monoammonium phosphate (MAP), diammonium phosphate (DAP), triple superphosphate (TSP), and RP] on corn (Zea mays L.) response in two consecutive growing seasons in a P-deficient, silt-loam soil (Aquic Fraglossudalfs) in eastern Arkansas. Averaged across years, corn yield was numerically largest from ECST (12.9 Mg ha–1), which differed (P < 0.05) from all other treatments and was numerically smallest from DAP (10.1 Mg ha–1), which was similar to MAP (10.7 Mg ha–1), CPST (10.3 Mg ha–1), and RP (10.3 Mg ha–1). Corn yield and kernel P uptake from ECST were at least 1.2 times greater (P < 0.05) than from CPST, TSP, DAP, and RP. Yield from ECST was 1.2 times greater (P < 0.05) than from MAP. A partial budget analysis showed that, across both years, fertilizer-P treatment net revenues for ECST were greater than those associated with the other fertilizer-P sources. Results demonstrated that wastewater-recovered struvite materials have the potential to be a sustainable source of P for corn production in P-deficient, silt-loam soil from both a technical and economic perspective. 

Phosphorus (P) recovery from wastewaters as struvite (MgNH4PO4·6H2O) may be a viable alternative fertilizer-P source for agriculture. The objective of this study was to evaluate the economic and environmental implications of struvite as a fertilizer-P source for flood-irrigated rice (Oryza sativa) relative to other commonly used commercially available fertilizer-P sources. A field study was conducted in 2019 and 2020 to evaluate the effects of wastewater-recovered struvite (chemically precipitated struvite (CPST) and electrochemically precipitated struvite (ECST)) on rice yield response in a P-deficient, silt–loam soil in eastern Arkansas relative to triple superphosphate, monoammonium and diammonium phosphate, and rock phosphate. A life cycle assessment methodology was used to estimate the global warming potentials associated with rice produced with the various fertilizer-P sources. Life cycle inventory data were based on the field trials conducted with and without struvite application for both years. A partial budget analysis showed that, across both years, net revenues for ECST and CPST were 1.4 to 26.8% lower than those associated with the other fertilizer-P sources. The estimated greenhouse gas emissions varied between 0.58 and 0.70 kg CO2 eq kg rice−1 from CPST and between 0.56 and 0.81 kg CO2 eq kg rice−1 from ECST in 2019 and 2020, respectively, which were numerically similar to those for the other fertilizer-P sources in 2019 and 2020. The similar rice responses compared to commercially available fertilizer-P sources suggest that wastewater-recovered struvite materials might be an alternative fertilizer-P-source option for flood-irrigated rice production if struvite can become price-competitive to other fertilizer-P sources. 

In this study, a suite of natural wastewater sources is tested to understand the effects of wastewater composition and source on electrochemically driven nitrogen and phosphorus nutrient removal. Kinetics, electrode behavior, and removal efficiency were evaluated during electrochemical precipitation, whereby a sacrificial magnesium (Mg) anode was used to drive precipitation of ammonium and phosphate. The electrochemical reactor demonstrated fast kinetics in the natural wastewater matrices, removing up to 54% of the phosphate present in natural wastewater within 1 min, with an energy input of only 0.04 kWh.m−3. After 1 min, phosphate removal followed a zero-order rate law in the 1 min - 30 min range. The zero-order rate constant (k) appears to depend upon differences in wastewater composition, where a faster rate constant is associated with higher Cl− and NH4+ concentrations, lower Ca2+ concentrations, and higher organic carbon content. The sacrificial Mg anode showed the lowest corrosion resistance in the natural industrial wastewater source, with an increased corrosion rate (vcorr) of 15.8 mm.y−1 compared to 1.9–3.5 mm.y−1 in municipal wastewater sources, while the Tafel slopes (β) showed a direct correlation with the natural wastewater composition and origin. An overall improvement of water quality was observed where important water quality parameters such as total organic carbon (TOC), total suspended solids (TSS), and turbidity showed a significant decrease. An economic analysis revealed costs based upon experimental Mg consumption are estimated to range from 0.19 $.m−3 to 0.30 $.m−3, but costs based upon theoretical Mg consumption range from 0.09 $.m−3 to 0.18 $.m−3. Overall, this study highlights that water chemistry parameters control nutrient recovery, while electrochemical treatment does not directly produce potable water, and that economic analysis should be based upon experimentally-determined Mg consumption data.