Soils of former Manufactured Gas Plants (MGPs) are often contaminated with iron-cyanide (Fe-CN) complexes that originate from gas purification process. Cyanide is a potentially toxic substance and its presence in soil and groundwater may cause risk for human health as well as for the environment. MGPs were commonly built on the city suburban areas, which have spread ever since. Nowadays, these sites are typically located in inner cities, causing environmental thread, due to the leaching of pollutants. More recently, columns and batch experiments have been used to study fate and mobility of contaminants is soil. The release of iron-cyanide complexes under unsaturated flow conditions was evaluated with eight columns of 30 cm length and a diameter of 5,4 cm. Cyanide concentrations in the collected leachates were measured with Flow Injection Analysis (FIA). Additionally pH, electrical conductivity (EC) and various ion concentrations were determined. In order to compare the release of Fe-CN complexes in saturated conditions a batch experiment was conducted, where in defined time intervals, 1 ml of the extract water phase was analyzed for CN concentration. Study revealed an analogous trend of cyanide release in both experiments indicating primarily the release of formerly dissolved phase (hexacyanoferrates) followed by continual dissolution of ferric ferrocyanide. We conclude that batch experiments, conducted prior to column analysis, can serve as preliminary prediction of the water soluble cyanide fraction under unsaturated conditions.
In Germany, at more than 1000 sites, soil is polluted with an anthropogenic contaminant in form of iron-cyanide complexes. These contaminations are caused by former Manufactured Gas Plants (MGPs), where electricity for lighting was produced in the process of coal gasification. The production of manufactured gas was restrained in 1950, which caused cessation of MGPs. Our study describes the application of Polychromix Handheld Field Portable Near-Infrared (NIR) Analyzer to predict the cyanide concentrations in soil. In recent times, when the soil remediation is of major importance, there is a need to develop rapid and non-destructive methods for contaminant determination in the field. In situ analysis enables determination of ‘hot spots’, is cheap and time saving in comparison to laboratory methods. This paper presents a novel usage of NIR spectroscopy, where a calibration model was developed, using multivariate calibration algorithms, in order to determine NIR spectral response to the cyanide concentration in soil samples. As a control, the contaminant concentration was determined using conventional Flow Injection Analysis (FIA). The experiments revealed that portable near-infrared spectrometers could be a reliable device for identification of contamination ‘hot spots’, where cyanide concentration are higher than 2400
mg kg-1 in the field and >1750 mg kg-1 after sample preparation in the laboratory, but cannot replace traditional laboratory analyses due to high limits of detection.
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 reme- diation strategies, it is relevant to understand the contaminant’s fate and transport in soil, and to quantify and mathe- matically 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 fer- ricyanides. 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.