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Vicinities of manufactured gas plants were often contaminated with solid iron–cyanide complexes
as a result of the coal gasification process. During the remediation of affected soils, knowledge about contaminant concentrations is crucial, but laboratory methods are often expensive and time consuming. Rapid and non-destructive field methods for contaminant determination permit an analysis of large sample numbers and hence, facilitate identification of ‘hot spots’ of contamination. Diffuse near infrared reflectance spectroscopy has proven to be a reliable analytical tool in soil investigation. In order to determine the feasibility of a Polychromix Handheld Field Portable Near-Infrared Analyzer (FP NIR), various sample preparation methods were examined, including homogenizing, sieving, drying, and grinding. Partial least squares calibration models were developed to determine near infrared (NIR) spectral responses to the cyanide concentration in the soil samples. As a control, the contaminant concentration
was determined using conventional flow injection analysis. The experiments revealed that portable
near-infrared spectrometers could be a reliable device for detecting cyanide concentrations >2,400 mgkg−1 in the field and >1,750 mgkg−1 after sample preparation in the laboratory.We found that portable NIR spectrometry cannot replace traditional laboratory analyses due to high limits of detection, but that it could be used for identification of contamination ‘hot spots’.
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.
Detection and behavior of iron-cyanide complexes in soils of a former Manufactured Gas Plant site
(2014)
In Germany, soil and groundwater atmore than a thousand sites are contaminatedwith ironcyanide complexes. These contaminations originate from the gas purification p process that was conducted inManufactured Gas Plants (MGP).There is a risk of human threat depending on the stability dissolved iron-cyanide complexes due to the potential release of toxic free cyanide, CN(aq) and HCN(g), (aq). The aim of this thesis was to evaluate a new method for the cyanide detection and to investigate the stability and retardation of the iron-cyanide complexes in soils by batch and column experiments in order to improve the knowledge concerning the fate of cyanide compounds in soil and groundwater. This study seeks for enhancing the efficiency of phytoremediation as a proper approach to decontaminate ironcyanides complexes and thus tries to make a contribution to environmental protection.
Soil contamination with iron-cyanide complexes is a common problem at former manufactured gas plant (MGP) sites. Dissolution of the cyanide, from Prussian Blue (ferric ferrocyanide), creates an environmental hazard, whereas the risk of groundwater contamination depends on the stability of dissolved iron–cyanide complexes. Lack of a standard leaching method to determine the water-soluble (plant-available) cyanide fraction generates potential limitations for implementing remediation strategies like phytoremediation. Applicability of neutral solution extraction to determine the water-soluble cyanide fraction and the stability of Prussian Blue in surface and near-surface soils of an MGP site in Cottbus, undersaturated and unsaturated water conditions, was studied in column leaching and batch extraction experiments. MGP soils used in the long-term tests varied according to the pH (5.0–7.7) and the total cyanide content (40–1718 mg kg−1). Column leaching, after four months of percolation, still yielded effluent concentrations exceeding the German drinking water limit (> 50 μg L−1) and the solubility of Prussian Blue reported in the literature (< 1 mg L−1) from both alkaline and acidic soils. Long-term (1344 h) extraction of MGP soils with distilled water was sufficient to dissolve 97% of the total cyanide from the slightly alkaline soils and up to 78% from the acidic soils. Both experiments revealed that dissolution of ferric ferrocyanide under circum-neutral pH and oxic water conditions is a function of time, where the released amount is dependent on the soil pH and total cyanide content. Unexpectedly high and continuous solubility of Prussian Blue, both in acidic and slightly alkaline MGP soils, implies the need to introduce an additional cyanide fraction (“readily soluble fraction”) to improve and specify cyanide leaching methods. Long-term extraction of cyanide-contaminated soil in neutral solution seems to be a promising approach to evaluate the potential hazard of groundwater pollution at the MGP sites.
Advancing performance of green technologies for remediation and reclamation of degraded urban soils
(2015)
The soil in the vicinities of former Manufactured Gas Plant (MGP) sites is commonly contaminated with iron-cyanide complexes (ferric ferrocyanide). The phenomenon of cyanide mobility in soil, according to the literature, is mainly governed by the dissolution and precipitation of ferric ferrocyanide, which is only slightly soluble (<1 mg L¡1) under acidic conditions. In this paper, retention properties of the sandy loam soil and the potential vertical movement of the solid iron-cyanide complexes, co-existing with the dissolution, sorption and precipitation reactions were investigated. Preliminary research conducted on a former MGP site implied colloidal transport of ferric ferricyanide from the initial deposition in the wastes layer towards the sandy loam material (secondary accumulation), which possibly retarded the mobility of cyanide (CN). A series of batch and column experiments were applied in order to investigate the retardation of iron-cyanide complexes by the sandy loam soil. Batch experiments revealed that in circumneutral pH conditions sandy loam material decreases the potassium ferro- and ferricyanide concentration. In column experiments a minor reduction in CN concentration was observed prior to addition of iron sulfide (FeS) layer, which induced the formation of the Prussian blue colloids in circumneutral pH conditions. Precipitated solid iron-cyanide complexes were mechanically filtered by the coherent structure of the investigated soil. Additionally, the reduction of the CN concentration of the percolation solutions by the sandy loam soil was presumably induced due to the formation of potassium manganese iron-cyanide (K2Mn[Fe(CN)6]).