Long-Term Release of Iron-Cyanide Complexes from the Soils of a Manufactured Gas Plant Site

Iron-cyanide (Fe-CN) complexes have been detected at Manufactured Gas Plant sites (MGP) worldwide. The risk of groundwater contamination depends mainly on the dissolution of ferric ferrocyanide. In order to design effective remediation strategies, it is relevant to understand the contaminant’s fate and transport in soil, and to quantify and mathematically model a release rate. The release of iron-cyanide complexes from four contaminated soils, originating from the former MGP in Cottbus, has been studied by using a column experiment. Results indicated that long-term cyanide (CN) release is governed by two phases: one readily dissolved and one strongly fixed. Different isotherm and kinetic equations were used to investigate the driving mechanisms for the ferric ferrocyanide release. Applying the isotherm equations assumed an approach by which two phases were separate in time, whereas the multiple first order equation considered simultaneous occurrence of both cyanide pools. Results indicated varying CN release rates according to the phase and soil. According to isotherm and kinetic models, the long-term iron cyanide release from the MGP soils is a complex phenomenon driven by various mechanisms parallely involving desorption, diffusion and transport processes. Phase I (rapid release) is presumably mainly constrained by the transport process of readily dissolved iron-cyanide complexes combined with desorption of CN bound to reactive heterogeneous surfaces that are in direct contact with the aqueous phase (outer-sphere complexation). Phase II (limited rate) is presumably driven by the diffusion controlled processes involving dissolution of precipitated ferric ferrocyanide from the mineral or inner-sphere complexation of ferricyanides. CN release rates in phase I and II were mainly influenced by the pH, organic matter (OM) and the total CN content. The cyanide release rates increased with increasing pH, decreased with low initial CN concentration and were retarded by the increase in OM content.

Impact of crystalline and amorphous iron-and aluminum hydroxides on mechanisms of phosphate adsorption and desorption

Fourier-transform infrared（FT-IR） spectroscopic experiments were carried out during phosphate adsorption on highly crystalline gibbsite, poorly crystalline 2-line-ferrihydrite and amorphous iron–aluminum–hydroxide mixtures in the molar ratio 1：0, 10：1, 5：1, 1：1, 1：5, 1：10 and 0：1. The OH stretching vibrational bands were utilized to analyze changes in structural and surface OH groups during adsorption, because the position of characteristic P／O vibrational bands can shift depending on reaction conditions, pH or adsorbed phosphate content.Adsorption and desorption kinetics were studied at pH6 and different initial phosphate concentrations to achieve varying phosphate coverage on the mineral surfaces. For gibbsite the formation of AlHPO4 and Al2HPO4 can be assumed, while for ferrihydrite, a FeHPO4 or Fe2PO4 complex and the precipitation of FePO4 with longer equilibration time were proposed.Fe2HPO4 or a Fe2PO4 surface complex was deduced for Fe-hydroxides, an AlH2PO4 surface complex was identified for Al-hydroxide, and both displayed either hydrogen bonds to neighboring hydroxyl groups or hydrogen bonds to outer-sphere complexes. Fe：Al-hydroxide mixtures with high Al ratios showed a low phosphate desorption rate, while ferrihydrite and the Fe：Al-hydroxide mixtures with high Fe ratios had almost negligible desorption rates. It was concluded that within the weakly associated amorphous FeO（OH） materials, FePO4 precipitated, which was bound by outer-sphere hydrogen bonds. With high Al ratios, desorption increased, which indicated weaker phosphate binding of both inner-sphere and outer-sphere complexes and hence, either no or minor quantities of precipitate. Ferrihydrite showed a more rigid structure and a lower extent of precipitation compared to amorphous Fe-hydroxide.

Phosphorus release from vivianite and hydroxyapatite by organic and inorganic compounds

Based on recent mining rates and the exhaustion of global phosphorus(P)reserves,there is a need to mobilize P already stored in soils,and its recovery from secondary resources such as Ca-and Fe-phosphates is important.The Ca-phosphate hydroxyapatite forms a good fertilizer source,while vivianite is formed in waterlogged soils and sediments.During sludge treatment,the formation of vivianite has been identified,being mainly Fe-phosphate.Long-term P release from both hydroxyapatite and vivianite was studied using different inorganic(CaCl2 and CaSO4)and organic(citric and humic acid)reagents during batch experiments.Reagents CaCl2 and CaSO4 represent the soil solution,while citric and humic acids as organic constituents affect P availability in the rhizosphere and during the process of humification.Additionally,the flow-through reactor(FTR)technique with an infinite sink was used to study the long-term P release kinetics.The cumulative P release was higher by organic acids than by inorganic compounds.The cumulative P release rates were higher in the FTR with CaCl2 as compared to the batch technique.The infinite sink application caused a continuously high concentration gradient between the solid and liquid phases,leading to higher desorption rates as compared to the batch technique.The predominant amount of the total P released over time was available for a short term.While inorganic anion exchange occurred at easily available binding sites,organic acids affected the more heavily available binding sites,which could be embedded within the mineral structure.The results showed that organic compounds,especially citric acid,play a superior role as compared to the inorganic constituents of the soil solution during the recovery of already stored P from the tertiary phosphates vivianite and hydroxyapatite.