ABSTRACT
Titanomagnetite (Fe(3-x)Ti(x)O(4)) nanoparticles were synthesized by room temperature aqueous precipitation, in which Ti(IV) replaces Fe(III) and is charge compensated by conversion of Fe(III) to Fe(II) in the unit cell. A comprehensive suite of tools was used to probe composition, structure, and magnetic properties down to site-occupancy level, emphasizing distribution and accessibility of Fe(II) as a function of x. Synthesis of nanoparticles in the range 0≤x≤0.6 was attempted; Ti, total Fe and Fe(II) content were verified by chemical analysis. TEM indicated homogeneous spherical 9-12 nm particles. µ-XRD and Mössbauer spectroscopy on anoxic aqueous suspensions verified the inverse spinel structure and Ti(IV) incorporation in the unit cell up to x≤0.38, based on Fe(II)/Fe(III) ratio deduced from the unit cell edge and Mössbauer spectra. Nanoparticles with a higher value of x possessed a minor amorphous secondary Fe(II)/Ti(IV) phase. XANES/EXAFS indicated Ti(IV) incorporation in the octahedral sublattice (B-site) and proportional increases in Fe(II)/Fe(III) ratio. XA/XMCD indicated that increases arise from increasing B-site Fe(II), and that these charge-balancing equivalents segregate to those B-sites near particle surfaces. Dissolution studies showed that this segregation persists after release of Fe(II) into solution, in amounts systematically proportional to x and thus the Fe(II)/Fe(III) ratio. A mechanistic reaction model was developed entailing mobile B-site Fe(II) supplying a highly interactive surface phase that undergoes interfacial electron transfer with oxidants in solution, sustained by outward Fe(II) migration from particle interiors and concurrent inward migration of charge-balancing cationic vacancies in a ratio of 3:1.
ABSTRACT
Although broiler (chicken, Gallus gallus domesticus) litter has long been used as a fertilizer, estimating the rate required to supply a desired amount of plant-available N is still hampered by the lack of rapid methods to estimate potentially mineralizable nitrogen (PMN). Previous research has suggested that near infrared reflectance spectroscopy (NIRS) and certain poultry litter characteristics, such as water-soluble organic nitrogen (WSON), may be useful for estimating PMN. The objectives of this study were to evaluate NIRS and WSON as tools to estimate PMN in broiler litter. Sixty sieved (2 mm) and freeze-dried broiler litter samples were mixed with Cowarts sandy loam soil (fine-loamy, kaolinitic, thermic Typic Kanhapludult) and incubated at 25 degrees C for 112 d. Cumulative net N mineralized with time was fitted to a single-pool exponential model to determine PMN for each broiler litter sample. The PMN values obtained were regressed against NIRS (780 to 2500 nm) and WSON measurements. We found strong relationships between measured- and NIRS-predicted PMN (R2 = 0.82), and between measured PMN and WSON (R2 = 0.87). These results demonstrate the feasibility of using either of these two methods to estimate PMN in broiler litter. Future work should further test both methods for their ability to estimate mineralizable N in whole, moist broiler litter under field conditions.
