Toward a Regional Phosphorus (Re)cycle in the US Midwest.

Redirecting anthropogenic waste phosphorus (P) flows from receiving water bodies to high P demand agricultural fields requires a resource management approach that integrates biogeochemistry, agronomy, engineering, and economics. In the US Midwest, agricultural reuse of P recovered from spatially colocated waste streams stands to reduce point-source P discharges, meet agricultural P needs, and-depending on the speciation of recovered P-mitigate P losses from agriculture. However, the speciation of P recovered from waste streams via its chemical transformation-referred to here as recovered P (rP) differs markedly based on waste stream composition and recovery method, which can further interact with soil and crop characteristics of agricultural sinks. The solubility of rP presents key tensions between engineered P recovery and agronomic reuse because it defines both the ability to remove organic and inorganic P from aqueous streams and the crop availability of rP. The potential of rP generation and composition differs greatly among animal, municipal, and grain milling waste streams due to the aqueous speciation of P and presence of coprecipitants. Two example rP forms, phytin and struvite, engage in distinct biogeochemical processes on addition to soils that ultimately influence crop uptake and potential losses of rP. These processes also influence the fate of nitrogen (N) embodied in rP. The economics of rP generation and reuse will determine if and which rP are produced. Matching rP species to appropriate agricultural systems is critical to develop sustainable and financially viable regional exchanges of rP from wastewater treatment to agricultural end users.

Spectroscopic, structural and computational analysis of [Re(CO)3(dippM)Br](n+) (dippM = 1,1'-bis(diiso-propylphosphino)metallocene, M = Fe, n = 0 or 1; M = Co, n = 1).

While the redox active backbone of bis(phosphino)ferrocene ligands is often cited as an important feature of these ligands in catalytic studies, the structural parameters of oxidized bis(phosphino)ferrocene ligands have not been thoroughly studied. The reaction of [Re(CO)3(dippf)Br] (dippf = 1,1'-bis(diiso-propylphosphino)ferrocene) and [NO][BF4] in methylene chloride yields the oxidized compound, [Re(CO)3(dippf)Br][BF4]. The oxidized species, [Re(CO)3(dippf)Br][BF4], and the neutral species, [Re(CO)3(dippf)Br], are compared using X-ray crystallography, cyclic voltammetry, visible spectroscopy, IR spectroscopy and zero-field (57)Fe Mössbauer spectroscopy. In addition, the magnetic moment of the paramagnetic [Re(CO)3(dippf)Br][BF4] was measured in the solid state using SQUID magnetometry and in solution by the Evans method. The electron transfer reaction of [Re(CO)3(dippf)Br][BF4] with acetylferrocene was also examined. For additional comparison, the cationic compound, [Re(CO)3(dippc)Br][PF6] (dippc = 1,1'-bis(diiso-propylphosphino)cobaltocenium), was prepared and characterized by cyclic voltammetry, X-ray crystallography, and NMR, IR and visible spectroscopies. Finally, DFT was employed to examine the oxidized dippf ligand and the oxidized rhenium complex, [Re(CO)3(dippf)Br](+).