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.
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’.
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.