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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.
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]).
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.
The continuous release of persistent iron-cyanide (Fe-CN) complexes from various industrial sources poses a high hazard to the environment and indicates the necessity to analyze a considerable amount of samples. Conventional flow injection analysis (FIA) is a time and cost consuming method for cyanide (CN) determination. Thus, a rapid and economic alternative needs to be developed to quantify the Fe-CN complexes. 52 soil samples were collected at a former Manufactured Gas Plant (MGP) site in order to determine the feasibility of diffuse reflectance infrared Fourier spectroscopy (DRIFTS). Soil analysis revealed CN concentrations in a range from 8 to 14.809 mg kg⁻¹, where 97% was in the solid form (Fe₄[Fe(CN)₆]₃), which is characterized by a single symmetrical CN band in the range 2092-2084 cm-1. The partial least squares (PLS) calibration-validation model revealed IR response to CNtot which exceeds 2306 mg kg⁻¹(limit of detection, LOD). Leave-one-out cross-validation (LOO-CV) was performed on soil samples, which contained low CNtot (<900 mg kg⁻¹). This improved the sensitivity of the model by reducing the LOD to 154 mg kg⁻¹. Finally, the LOO-CV conducted on the samples with CNtot > 900 mg kg⁻¹ resulted in LOD equal to 3751 mg kg⁻¹. It was found that FTIR spectroscopy provides the information concerning different CN species in the soil samples. Additionally, it is suitable for quantifying Fe-CN species in matrixes with CNtot > 154 mg kg⁻¹. Thus, FTIR spectroscopy, in combination with the statistical approach applied here seems to be a feasible and quick method for screening of contaminated sites.
Contaminated sites create a significant risk to human health, by poisoning drinking water, soil, air and as a consequence
food. Continuous release of persistent iron-cyanide (Fe-CN) complexes from various industrial sources poses a high hazard to the environment and indicates the necessity to analyze considerable amount of samples. At the present time quantitative determination of Fe-CN concentration in soil usually requires a time consuming two step process: digestion of the sample (e.g., micro distillation system) and its analytical detection performed, e.g., by automated spectrophotometrical flow injection analysis (FIA). In order to determine the feasibility of diffuse reflectance
infrared Fourier spectroscopy (DRIFTS) to quantify the Fe-CN complexes in soil matrix, 42 soil samples were collected (8 to 12.520 mg kg-1CN) indicating single symmetrical CN band in the range 2092 - 2084 cm-1. Partial least squares (PLS) calibration-validation model revealed IR response to CNtot exceeding 1268 mg kg-1 (limit of detection, LOD). Subsequently, leave-one-out cross-validation (LOO-CV) was performed on soil samples containing low CNtot (<900 mg kg-1), which improved the sensitivity of the model by reducing the LOD to 154 mg kg-1. Finally, the LOO-CV conducted on the samples with CNtot >900 mg kg-1 resulted in LOD equal to 3494 mg kg-1. Our results indicate that spectroscopic data in combination with PLS statistics can efficiently be used to predict Fe-CN concentrations in soil. We conclude that the protocol applied in this study can strongly reduce the time and costs essential for the spatial and vertical screening of the site affected by complexed Fe-CN.