Impact of iron–organic matter complexes on aqueous phosphate concentrations (original) (raw)
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Fractionation of oxygen isotopes in phosphate during its interactions with iron oxides
2010
Iron (III) oxides are ubiquitous in near-surface soils and sediments and interact strongly with dissolved phosphates via sorption, co-precipitation, mineral transformation and redox-cycling reactions. Iron oxide phases are thus, an important reservoir for dissolved phosphate, and phosphate bound to iron oxides may reflect dissolved phosphate sources as well as carry a history of the biogeochemical cycling of phosphorus (P). It has recently been demonstrated that dissolved inorganic phosphate (DIP) in rivers, lakes, estuaries and the open ocean can be used to distinguish different P sources and biological reaction pathways in the ratio of 18 O/ 16 O (d 18 O P) in PO 4 3À. Here we present results of experimental studies aimed at determining whether non-biological interactions between dissolved inorganic phosphate and solid iron oxides involve fractionation of oxygen isotopes in PO 4. Determination of such fractionations is critical to any interpretation of d 18 O P values of modern (e.g., hydrothermal iron oxide deposits, marine sediments, soils, groundwater systems) to ancient and extraterrestrial samples (e.g., BIF's, Martian soils). Batch sorption experiments were performed using varied concentrations of synthetic ferrihydrite and isotopically-labeled dissolved ortho-phosphate at temperatures ranging from 4 to 95°C. Mineral transformations and morphological changes were determined by X-Ray, Mö ssbauer spectroscopy and SEM image analyses. Our results show that isotopic fractionation between sorbed and aqueous phosphate occurs during the early phase of sorption with isotopically-light phosphate (P 16 O 4) preferentially incorporated into sorbed/solid phases. This fractionation showed negligible temperature-dependence and gradually decreased as a result of O-isotope exchange between sorbed and aqueousphase phosphate, to become insignificant at greater than $100 h of reaction. In high-temperature experiments, this exchange was very rapid resulting in negligible fractionation between sorbed and aqueous-phase phosphate at much shorter reaction times. Mineral transformation resulted in initial preferential desorption/loss of light phosphate (P 16 O 4) to solution. However, the continual exchange between sorbed and aqueous PO 4 , concomitant with this mineralogical transformation resulted again in negligible fractionation between aqueous and sorbed PO 4 at long reaction times (>2000 h). This finding is consistent with results obtained from natural marine samples. Therefore, 18 O values of dissolved phosphate (DIP) in sea water may be preserved during its sorption to iron-oxide minerals such as hydrothermal plume particles, making marine iron oxides a potential new proxy for dissolved phosphate in the oceans.
Chemosphere, 2019
Iron (oxyhydr)oxides (FeOx) control retention of dissolved nutrients and contaminants in aquatic systems. However, FeOx structure and reactivity is dependent on adsorption and incorporation of such dissolved species, particularly oxyanions such as phosphate and silicate. These interactions affect the fate of nutrients and metal(loids), especially in perturbed aquatic environments such as eutrophic coastal systems and environments impacted by acid mine drainage. Altered FeOx reactivity impacts sedimentary nutrient retention capacity and, eventually, ecosystem trophic state. Here, we explore the influence of phosphate (P) and silicate (Si) on FeOx structure and reactivity. Synthetic, poorly crystalline FeOx with adsorbed and coprecipitated phosphate or silicate at low but environmentally relevant P/Fe or Si/Fe ratios (0.02e0.1 mol mol1) was prepared by base titration of Fe(III) solutions. Structural characteristics of FeOx were investigated by X-ray diffraction, synchrotron-based X-ray absorption spectroscopy and high-energy X-ray scattering. Reactivity of FeOx was assessed by kinetic dissolution experiments under acidic (dilute HCl, pH 2) and circum-neutral reducing (bicarbonate-buffered ascorbic acid, pH 7.8, Eh ~ 300mV) conditions. At these loadings, phosphate and silicate coprecipitation had only slight impact on local and intermediate-ranged FeOx structure, but significantly enhanced the dissolution rate of FeOx. Conversely, phosphate and silicate adsorption at similar loadings resulted in particle surface passivation and decreased FeOx dissolution rates. These findings indicate that varying nutrient loadings and different interaction mechanisms between anions and FeOx (adsorption versus coprecipitation) can influence the broader biogeochemical functioning of aquatic ecosystems by impacting the structure and reactivity of FeOx.
Origins of life and evolution of the biosphere : the journal of the International Society for the Study of the Origin of Life, 2003
The present study is based on the proposal that if the aqueous phosphorus-capture mechanism by iron oxide precursors was inhibited in prebiotic anoxic scenarios then soluble phosphates could have been more available than what is observed now. Supporting this conjecture, we examine prevailing contemporary trapping mechanisms of orthophosphate (Pi) and pyrophosphate (PPi). To illustrate its efficiency, the attachment of (Pi) onto aggregates of iron-3 oxyhydroxide is compared with the one reported for the product of its condensation, PPi. The electrophoretic profiles of the Pi- and PPi-aggregate complexes reveal different pH-modulated interactions of the phosphorylated compounds with both the aggregate and its aqueous surrounding layers. The observed differences of Pi/PPi sorption and desorption mechanisms are discussed in terms of their consequences to the prebiotic availability of soluble orthophosphate and of a phosphorylated compound having the high-energy phosphoanhydride linkage ...
Phosphate complexation model and its implications for chemical phosphorus removal
Water environment research : a research publication of the Water Environment Federation, 2008
A phosphate complexation model is developed, in an attempt to understand the mechanistic basis of chemically mediated phosphate removal. The model presented here is based on geochemical reaction modeling techniques and uses known surface reactions possible on hydrous ferric oxide (HFO). The types of surface reactions and their reaction stoichiometry and binding energies (logK values) are taken from literature models of phosphate interactions with iron oxides. The most important modeling parameter is the proportionality of converting moles of precipitated HFO to reactive site density. For well-mixed systems and phosphate exposed to ferric chloride during HFO precipitation, there is a phosphate capacity of 1.18 phosphate ions per iron atom. In poorly mixed systems with phosphate exposed to iron after HFO formation, the capacity decreased to 25% of the well-mixed value. The same surface complexation model can describe multiple data sets, by varying only a single parameter proportional ...
Electron Microscopic Studies on Phosphate Binding Processes in the Presence of Iron
Advanced Materials Research, 2011
Phosphates are widely used as a substitute material for bones and teeth in medical sciences. It is known that phosphate and iron have a strong affinity for each other. In this study, process of formation of iron phosphate was closely monitored using scanning electron microscope equipped with backscatter electron image and energy dispersive X-ray imaging facilities. Different stages of formation of the iron-phosphate material in an environment rich in phosphate and iron were observed. Initial stage of absorbing iron on phosphate-rich substrate is the most important stage of the entire process. X-ray mapping provides strong visual evidence to track down the dispersion of major elements during this process.
Journal of Agricultural and Food Chemistry, 2005
The aim of this work is to study the suitability of the complementary use of ultrafiltration (UF) and the interaction with an anion-exchange resin (AR) to characterize of phosphate-metal-humic complexes in solution. The results indicate that a methodological approach consisting of the validation and calibration of the AR method by the UF method and the further use of the AR method is suitable for characterizing phosphate-metal complexes. Such an approach has proven to be useful for calculating the phosphate maximum binding capacity of iron-humic complexes and stability constants. It might also be used to obtain valuable purified phosphate-metal-humic complexes for further structural characterization.
Environmental Geology, 2004
Different methods were compared to evaluate the oxidation capacity of ferric iron in column studies. The specific adsorption of the reactive tracer phosphate on the Fe(III) oxide surface was used as an alternative approach to determine the oxidation capacity utilizing the linear correlation between the long-term extent of Fe(III) reduction and the specific surface area of the oxide. Although a low crystalline form of ferric iron (twoline ferrihydrite) was used as electron acceptor and toluene as a carbon source, only 31 and 24% respectively of the total iron was reduced by Geobacter metallireducens in parallel experiments. The results of the phosphate tracer tests were in good agreement with the Fe(III) that was actually reduced and the microbially oxidized toluene. The oxidation capacity of ferric iron is therefore overestimated by the chemical extraction methods, which completely dissolve the ferrihydrite and neglect surface-dependent limitations.
Journal of environmental sciences (China), 2016
Iron oxide (FeO) coated by natural organic matter (NOM) is ubiquitous. The associations of minerals with organic matter (OM) significantly changes their surface properties and reactivity, and thus affect the environmental fate of pollutants, including nutrients (e.g., phosphorus (P)). In this study, ferrihydrite/goethite-humic acid (FH/GE-HA) complexes were prepared and their adsorption characteristics on P at various pH and ionic strength were investigated. The results indicated that the FeO-OM complexes showed a decreased P adsorption capacity in comparison with bare FeO. The maximum adsorption capacity (Qmax) decreased in the order of FH (22.17mg/g)>FH-HA (5.43mg/g)>GE (4.67mg/g)>GE-HA (3.27mg/g). After coating with HA, the amorphous FH-HA complex still showed higher P adsorption than the crystalline GE-HA complex. The decreased P adsorption observed might be attributed to changes of the FeO surface charges caused by OM association. The dependence of P adsorption on the ...
2005
Inositol phosphates are metabolically derived organic phosphates that increasingly appear to be an important sink and source of phosphate in the environment. Inositol hexakis dihydrogen phosphate or phytic acid is the most common inositol phosphate in the environment. Iron is abundant in many terrestrial systems. Mobility of phytic acid iron complexes are potentially pH and redox responsive. Ferric and ferrous complexes of phytic acid were investigated by proton nuclear magnetic resonance spectroscopy, enzymatic dephosphoralation and potentiometrically in solution. The redox potential and concentration of iron were measured in a soil column containing a benchmark poorly drained soil from Maryland (Elkton). Ferrous phytate was found to form quickly and persist for a longer period then ferric phytate. Dissociation constants were 1.113 and 1.186 and formation constants were 0.899 and 0.843 for ferric and ferrous phytate respectively. Enzymatic dephosphoralation recoveries supported the magnitude of the kinetic and equilibrium rate constants.