The forms of bioavailability of phosphorus in integrated vertical flow constructed wetland with earthworms and different substrates

A sequential extraction method was utilized to analyze seven forms of P in an integrated vertical-flow constructed wetland (IVFCW) containing earthworms and different substrates. The aluminum-bound P (Al-P) content was found to be lower, and the occluded P (Oc-P) content was higher in the IVFCW. The addition of earthworms into the influent chamber of IVFCW increased the exchange P (Ex-P), iron-bound P (Fe-P), calcium bound P (Ca-P), Oc-P, detritus-bound (De-P) and organic P (Org-P) content in the influent chamber, and also enhanced P content uptake by wetland plants. A significantly positive correlation between P content of above-ground wetland plants and the Ex-P, Fe-P, Oc-P and Org-P content in the rhizosphere was found (P < 0.05), which indicated that the Ex-P, Fe-P, Oc-P and Org-P could be bio-available P. The Ex-P, Fe-P, De-P, Oc-P and Ca-P content of the influent chamber was higher where the substrate contained a mixture of Qing sand and river sand rather than only river sand. Also the IVFCW with earthworms and both Qing sand and river sand had a higher removal efficiency of P, which was related to higher P content uptake by wetland plants and P retained in IVFCW. These findings suggest that addition of earthworms in IVFCW increases the bioavailable P content, resulting in enhanced P content uptake by wetland plants.

Reaction of (±)-1,1′-binaphthyl-2,2′-diyl hydrogen phosphate {(±)-phosH} with copper(II), cobalt(II) and iron(II) compounds; Identification by x-ray diffraction of [Co(CH3OH)4(H2O)2][(+)-phos][(−)-phos]. 2CH3OH·H2O

[Cu2(μO2CCH3)4(H2O)2], [CuCO3·Cu(OH)2], [CoSO4·7H2O], [Co((+)-tartrate)], and [FeSO4·7H2O] react with excess racemic (±)- 1,1′-binaphthyl-2,2′-diyl hydrogen phosphate {(±)-PhosH} to give mononuclear CuII, CoII and FeII products. The cobalt product, [Co(CH3OH)4(H2O)2]((+)-Phos)((−)-Phos) ·2CH3OH·H2O (7), has been identified by X-ray diffraction. The high-spin, octahedral CoII atom is ligated by four equatorial methanol molecules and two axial water molecules. A (+)- and a (−)-Phos− ion are associated with each molecule of the complex but are not coordinated to the metal centre. For the other CoII, CuII and FeII samples of similar formulation to (7) it is also thought that the Phos− ions are not bonded directly to the metal. When some of the CuII and CoII samples are heated under high vacuum there is evidence that the Phos− ions are coordinated directly to the metals in the products.

Ferric and ferrous iron in nitroso-myoglobin: computer simulations of stable and metastable states and their infrared spectra

The binding of NO to iron is involved in the biological function of many heme proteins. Contrary to ligands like CO and O-2, which only bind to ferrous (Fe-II) iron, NO binds to both ferrous and ferric (Fe-II) iron. In a particular protein, the natural oxidation state can therefore be expected to be tailored to the required function. Herein, we present an ob initio potential-energy surface for ferric iron interacting with NO. This potential-energy surface exhibits three minima corresponding to eta'-NO coordination (the global minimum), eta(1)-ON coordination and eta(2) coordination. This contrasts with the potential-energy surface for Fe-II-NO, which ex- hibits only two minima (the eta(2) coordination mode for Fe-II is a transition state, not a minimum). In addition, the binding energies of NO are substantially larger for Fe-III than for Fe-II. We have performed molecular dynamics simulations for NO bound to ferric myoglobin (Mb(III)) and compare these with results obtained for Mb(II). Over the duration of our simulations (1.5 ns), all three binding modes are found to be stable at 200 K and transiently stable at 300 K, with eventual transformation to the eta(1)-NO global-minimum conformation. We discuss the implication of these results related to studies of rebinding processes in myoglobin.