Degradation of ferrocyanide by natural isolated bacteria.

This study aims at investigating the iron cyanide (CN) degradation potential of two natural bacterial isolates with the purpose of their application in iron CN phytoremediation. The strains were isolated from contaminated soil and incubated over 4 months with 50 mg L-1 CN (as ferrocyanide) as the sole iron and nitrogen source. Unlike previous reports, the study provides control for bacterial growth, biotic and abiotic CN losses. Bacterial growth, CN, ammonium, and nitrate concentrations were monitored regularly. Both strains grew less rapid with iron CN compared with the positive control. However, the growth was diauxic. The CN concentration in the media decreased with 20% and 25% respectively, while that in the sterile controls remained stable. Ammonium was detected in the media of both strains implying that a fraction of the initially applied ferrocyanide has been converted. The nitrogen lost from the system evened out with that in the cells at the end of the experiments. These results showed that the investigated strains were undoubtedly able to grow on iron CN as an alternative nitrogen source, but contrary to some previous findings, the iron CN utilization is much slower and takes place only after complete exhaustion of the cellular nitrogen reserves.

Detoxification of ferrocyanide in asoil-plant system.

The detoxification of iron cyanide in a soil-plant system was investigated to assess the total cyanide extracted from contaminated soil and allocated in the leaf tissue of willow trees (Salix caprea). They were grown in soil containing up to 1000 mg/kg dry weight (dw) of cyanide (CN), added as 15N-labeled potassium ferrocyanide and prepared with a new method for synthesis of labeled iron cyanides. CN content and 15N enrichment were monitored weekly over the exposure in leaf tissue of different age. The 15N enrichment in the young and old leaf tissue reached up to 15.197‰ and 9063‰, respectively; it increased significantly over the exposure and with increasing exposure concentrations (p < 0.05). Although the CN accumulation in the old leaf tissue was higher, compared to the young leaf tissue (p < 0.05), the 15N enrichment in the two tissue types did not differ statistically. This indicates a non-uniform CN accumulation but a uniform 15N allocation throughout the leaf mass. Significant differences were detected between the measured CN content and the C15N content, calculated from the 15N enrichment (p < 0.05), revealing a significant CN fraction within the leaf tissue, which could not be detected as ionic CN. The application of labeled iron CN clearly shows that CN is detoxified during uptake by the willows. However, these results do not exclude other detoxification pathways, not related to the trees. Still, they are strongly indicative of the central role the trees played in CN removal and detoxification under the experimental conditions.

Retardation of iron-cyanide complexes in the soil of a former manufactured gas plant site.

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]).

Uptake of ferrocyanide in willow and poplar trees in a long term greenhouse experiment.

Phytoremediation of sites contaminated with iron cyanides can be performed using poplar and willow trees. Poplar and willow trees were grown in potting substrate spiked with ferrocyanide concentrations of up to 2,000 mg kg(-1) for 4 and 8 weeks respectively. Soil solution and leaf tissue of different age were sampled for total cyanide analysis every week. Chlorophyll content in the leaves was determined to quantify cyanide toxicity. Results showed that cyanide in the soil solution of spiked soils differed between treatments and on weekly basis and ranged from 0.5 to 1,200 mg l(-1). The maximum cyanide content in willow and poplar leaves was 518 mg kg(-1) fresh weight (FW) and 148 mg kg(-1) FW respectively. Cyanide accumulated in the leaves increased linearly with increasing cyanide concentration in the soil solution. On the long term, significantly more cyanide was accumulated in old leaf tissue than in young tissue. Chlorophyll content in poplar decreased linearly with increasing cyanide in the soil solution and in leaf tissue, and over time. The inhibitory concentration (IC50) value for poplars after 4 weeks of exposure was 173 mg l(-1) and for willow after 8 weeks of exposure-768 mg l(-1). Results show that willows tolerate much more cyanide and over a longer period than poplars, making them very appropriate for remediating sites highly contaminated with iron cyanides.

Disposal of coal combustion residues in terrestrial systems: contamination and risk management.

The world's ever-growing energy demand will lead to the installation of new coal-fired power plants. At least part of the coal combustion residue (CCR) generated in the coming years will be disposed of, adding to the large number of CCR disposal sites generated in the past and reinforcing the need for sound assessment and management of associated risks. Physical and chemical composition of CCR varies considerably depending on the quality of the feed coal, the combustion technology, fraction considered, and the method of disposal. Related risk pathways include (i) aerial routes, i.e., dust resuspension (Cr(VI)), emanation of radioactivity (Rn associated with U and Th series), and Hg volatilization threatening animal and human health; (ii) phytoaccumulation (B, Se, Mo, As) and plant toxicity (B) with subsequent effects on animals (e.g., Mo-induced hypocuprosis, As and Se toxicity) and humans (e.g., selenosis; food chain); and (iii) effluent discharge and percolation to groundwater and rivers (suspended solids, unfavorable pH, high Se, B, Hg, and As(III) concentrations). Recent and projected changes of CCR composition due to emerging clean coal technologies require close monitoring as the concentration of volatile elements such as Hg and Se, solubility (Hg, Cd, Cu) and volatilization (Hg, NH(3)) of some pollutants are likely to increase because of higher retention in certain fractions of CCRs and concurrent changes in pH (e.g., by mineral carbonation) and NH(3) content. These changes require additional research efforts to explore the implications for CCR quality, use, and management of risk associated with disposal sites.

Environmental risks of farmed and barren alkaline coal ash landfills in Tuzla, Bosnia and Herzegovina.

The disposal of coal combustion residues (CCR) has led to a significant consumption of land in the West Balkan region. In Tuzla (Bosnia and Herzegovina) we studied previously soil-covered (farmed) and barren CCR landfills including management practises, field ageing of CCR and the transfer of trace elements into crops, wild plants and wastewaters. Soil tillage resulted in mixing of cover soil with CCR. Medicago sativa showed very low Cu:Mo ratios (1.25) which may cause hypocuprosis in ruminants. Total loads of inorganic pollutants in the CCR transport water, but not pH ( approximately 12), were below regulatory limits of most EU countries. Arsenic concentrations in CCR transport water were <2microgl(-1) whereas reductive conditions in an abandoned landfill significantly enhanced concentrations in leachates (44microgl(-1)). The opposite pattern was found for Cr likely due to large initial leaching of CrVI. Public use of landfills, including farming, should be based on a prior risk assessment due to the heterogeneity of CCR.