Iron oxidation kinetics and phosphate immobilization along the flow-path from groundwater into surface water
Grift, B. van der; Rozemeijer, J.C. ; Griffioen, J. ; Velde, Y. van der - \ 2014
Hydrology and Earth System Sciences 18 (2014)11. - ISSN 1027-5606 - p. 4687 - 4702.
suspended sediment - ferrous iron - fresh-water - phosphorus limitation - nutrient dynamics - fe(ii) oxidation - arsenic removal - natural-waters - riparian zone - river
The retention of phosphorus in surface waters through co-precipitation of phosphate with Fe-oxyhydroxides during exfiltration of anaerobic Fe(II) rich groundwater is not well understood. We developed an experimental field set-up to study Fe(II) oxidation and P immobilization along the flow-path from groundwater into surface water in an agricultural experimental catchment of a small lowland river. We physically separated tube drain effluent from groundwater discharge before it entered a ditch in an agricultural field. Through continuous discharge measurements and weekly water quality sampling of groundwater, tube drain water, exfiltrated groundwater, and surface water, we investigated Fe(II) oxidation kinetics and P immobilization processes. The oxidation rate inferred from our field measurements closely agreed with the general rate law for abiotic oxidation of Fe(II) by O-2. Seasonal changes in climatic conditions affected the Fe(II) oxidation process. Lower pH and lower temperatures in winter (compared to summer) resulted in low Fe oxidation rates. After exfiltration to the surface water, it took a couple of days to more than a week before complete oxidation of Fe(II) is reached. In summer time, Fe oxidation rates were much higher. The Fe concentrations in the exfiltrated groundwater were low, indicating that dissolved Fe(II) is completely oxidized prior to inflow into a ditch. While the Fe oxidation rates reduce drastically from summer to winter, P concentrations remained high in the groundwater and an order of magnitude lower in the surface water throughout the year. This study shows very fast immobilization of dissolved P during the initial stage of the Fe(II) oxidation process which results in P-depleted water before Fe(II) is completely depleted. This cannot be explained by surface complexation of phosphate to freshly formed Fe-oxyhydroxides but indicates the formation of Fe(III)-phosphate precipitates. The formation of Fe(III)-phosphates at redox gradients seems an important geochemical mechanism in the transformation of dissolved phosphate to structural phosphate and, therefore, a major control on the P retention in natural waters that drain anaerobic aquifers.
Homogeneous, heterogeneous and biological oxidation of iron(II) in rapid sand filtration
Beek, C.G.E.M. van; Hiemstra, T. ; Hofs, B. ; Nederlof, M.M. ; Paassen, J.A.M. van; Reijnen, G.K. - \ 2012
Journal of Water Services Research and Technology-Aqua 61 (2012)1. - ISSN 0003-7214 - p. 1 - 13.
ferrous iron - fe(ii) oxidation - gallionella-ferruginea - isotope fractionation - metal (hydr)oxides - aqueous systems - organic-matter - atom exchange - ground-water - kinetics
Homogeneous, heterogeneous and biological oxidation may precipitate iron(II) as iron(III) hydroxides. In this paper we evaluate the conditions under which each of these processes is dominant in rapid sand filtration (RSF). It is demonstrated that in the presence of iron(III) hydroxide precipitates homogeneous oxidation is negligible compared with heterogeneous oxidation. As soon as iron oxidizing bacteria (IOB) are present, biological oxidation may contribute substantially, in particular under conditions of slight acidity and low oxygen concentration. As the oxidation step is preceded by an adsorption/uptake step, the competition between heterogeneous and biological oxidation is not determined by the oxidation rate, but by the adsorption or uptake rate. Extracellular polymeric substance (EPS), excreted by all kinds of bacteria, may serve as an initial adsorbent for dissolved iron(II) and iron(III) hydroxides. Because adsorption and oxidation of iron (II) either on biofilms (or EPS) or on mineral surfaces, are chemical processes, 'EPS iron oxidation' is not considered as a biological process. The so-called 'biological iron oxidation' actually refers to a treatment method characterized by high filtration rates and limited oxygen supply, where iron(II) is removed mainly by heterogeneous oxidation. The contribution of oxidation of iron(II) by IOB in this method is variable and may even be absent.
Colloid formation in groundwater by subsurface aeration: characterisation of the geo-colloids and their counterparts
Wolthoorn, A. ; Temminghoff, E.J.M. ; Riemsdijk, W.H. van - \ 2004
Applied Geochemistry 19 (2004)9. - ISSN 0883-2927 - p. 1391 - 1402.
lepidocrocite surface - fe(ii) oxidation - eutrophic lake - scanning force - iron removal - phosphate - goethite - adsorption - transport - media
Subsurface aeration is used to oxidise Fe in situ in groundwater to make the water potable. In a groundwater system with pH > 7, subsurface aeration results in a non-mobile Fe precipitate and mobile Fe colloids. Since originally the goal of subsurface aeration is to remove Fe in situ, the formation of non-mobile Fe precipitate is the desired result. In addition to this intended effect, subsurface aeration may also strongly enhance the microbiological removal of NH4 in the purification station. A hypothesis is that mobile Fe colloids may be the link between subsurface aeration and the positive effect on the microbiological removal of NH4. The objective of this study is to characterise the mobile Fe colloids and to derive a synthetic substitute for the naturally formed Fe colloids in order to be able to apply the Fe colloids as a management tool to enhance the removal of NH4 in the process of producing drinking water from groundwater. At a purification station in The Netherlands natural Fe colloids from an aerated well were sampled. Furthermore, eight synthetic Fe colloids were prepared by oxidising synthetic solutions differing in elemental composition. The colloids were analysed using chemical analysis and electron microscopy (SEM and SEM-EDAX). The Fe colloids sampled in the field contained Fe, Ca, Na, PO4 and Mn. Also in the synthetic Fe colloids PO4, Ca, Na and Mn were the most important elements next to Fe. Phosphate and dissolved organic C strongly influenced the morphology of the synthetic Fe colloids. When both the elemental composition and the morphology of the Fe colloids are taken into account, the synthetic Fe colloids formed in the synthetic solution containing Fe, Mn, PO4, SiO4 and dissolved organic matter best match the Fe colloids from the field. (C) 2004 Elsevier Ltd. All rights reserved.
Colloid formation in groundwater: effect of phosphate, manganese, silicate and dissolved organic matter on the dynamic heterogeneous oxidation of ferrous iron
Wolthoorn, A. ; Temminghoff, E.J.M. ; Weng, L.P. ; Riemsdijk, W.H. van - \ 2004
Applied Geochemistry 19 (2004)4. - ISSN 0883-2927 - p. 611 - 622.
competitive adsorption - lepidocrocite surface - neutral solutions - fe(ii) oxidation - humic substances - eutrophic lake - gamma-feooh - oxygenation - transport - kinetics
Subsurface aeration is the in situ oxidation of Fe from groundwater that is used to make drinking water potable. When subsurface aeration is applied to an anaerobic groundwater system with pH > 7, Fe(II) is oxidised heterogeneously. The heterogeneous oxidation of Fe(II) can result in the in situ formation of Fe colloids. To study this, the effect of substances commonly found in groundwater (e.g. PO4, Mn, silicate and fulvic acid) on the heterogeneous oxidation process was measured. The heterogeneous oxidation of Fe(II) becomes retarded when PO4, Mn, silicate or fulvic acid is present in the groundwater in addition to Fe(II). Phosphate and fulvic acid retarded the oxidation process most. The heterogeneous oxidation was described using a model with a homogeneous (k(1)) and an autocatalytic oxidation rate constant (k'(2)). From the modelling it followed that the homogeneous oxidation rate constant was not affected or even slightly elevated whereas the autocatalytic oxidation rate constant decreased remarkably by the addition of PO4, Mn, silicate or fulvic acid. From speciation calculations it followed that the decreased availability of the Fe(H) species can only explain a small part of the retarded autocatalytic oxidation process. Therefore exploratory calculations were performed to gain insight into whether the adsorption of PO4 or fulvic acid could explain the retarded autocatalytic oxidation. These calculations showed that the adsorption of fulvic acid could explain the retarded autocatalytic oxidation process. In contrast the adsorption of PO4 only partly explained the retarded autocatalytic oxidation process. In terms of colloid formation this study shows that the heterogeneous oxidation of Fe(II) in presence of PO4, Mn, silicate or fulvic acid leads to the formation of Fe colloids. (C) 2003 Elsevier Ltd. All rights reserved.