skip to main content
OSTI.GOV title logo U.S. Department of Energy
Office of Scientific and Technical Information

Title: In situ treatment of cyanide-contaminated groundwater by iron cyanide precipitation

Abstract

Groundwater contamination with cyanide is common at many former or active industrial sites. Metal-cyanide complexes typically dominate aqueous speciation of cyanide in groundwater systems, with iron-cyanide complexes often most abundant. Typically, metal-cyanide complexes behave as nonadsorbing solutes in sand-gravel aquifer systems in the neutral pH range, rendering cyanide relatively mobile in groundwater systems. Groundwater pump-and-treat systems have often been used to manage cyanide contamination in groundwater. This study examined the feasibility of using in situ precipitation of iron cyanide in a reactive barrier to attenuate the movement of cyanide in groundwater. Laboratory column experiments were performed in which cyanide solutions were passed through mixtures of sand and elemental iron filings. Removal of dissolved cyanide was evaluated in a variety of cyanide-containing influents under various flow rates and sand-to-iron weight ratios. Long-term column tests performed with various cyanide-containing influents under both oxic and anoxic conditions, at neutral pH and at flow rates typical of sand-gravel porous media, yielded effluent concentrations of total cyanide as low as 0.5 mg/L. Effluent cyanide concentrations achieved were close to the solubilities of Turnbull's blue-hydrous ferric oxide solid solutions, indicating co-precipitation of the two solids. Maximum cyanide removal efficiency was achieved with approximately 10% by weightmore » of iron in the sand-iron mixtures; higher iron contents did not increase removal efficiency significantly. Results obtained indicate that in situ precipitation is a promising passive treatment approach for cyanide in groundwater.« less

Authors:
; ; ;
Publication Date:
OSTI Identifier:
20001045
Resource Type:
Journal Article
Resource Relation:
Journal Name: Water Environment Research; Journal Volume: 71; Journal Issue: 6; Other Information: PBD: Sep-Oct 1999
Country of Publication:
United States
Language:
English
Subject:
01 COAL, LIGNITE, AND PEAT; COAL GASIFICATION PLANTS; CYANIDES; IN-SITU PROCESSING; REMEDIAL ACTION; IRON; WATER POLLUTION CONTROL; GROUND WATER

Citation Formats

Ghosh, R.S., Dzombak, D.A., Luthy, R.G., and Smith, J.R. In situ treatment of cyanide-contaminated groundwater by iron cyanide precipitation. United States: N. p., 1999. Web. doi:10.2175/106143096X122456.
Ghosh, R.S., Dzombak, D.A., Luthy, R.G., & Smith, J.R. In situ treatment of cyanide-contaminated groundwater by iron cyanide precipitation. United States. doi:10.2175/106143096X122456.
Ghosh, R.S., Dzombak, D.A., Luthy, R.G., and Smith, J.R. 1999. "In situ treatment of cyanide-contaminated groundwater by iron cyanide precipitation". United States. doi:10.2175/106143096X122456.
@article{osti_20001045,
title = {In situ treatment of cyanide-contaminated groundwater by iron cyanide precipitation},
author = {Ghosh, R.S. and Dzombak, D.A. and Luthy, R.G. and Smith, J.R.},
abstractNote = {Groundwater contamination with cyanide is common at many former or active industrial sites. Metal-cyanide complexes typically dominate aqueous speciation of cyanide in groundwater systems, with iron-cyanide complexes often most abundant. Typically, metal-cyanide complexes behave as nonadsorbing solutes in sand-gravel aquifer systems in the neutral pH range, rendering cyanide relatively mobile in groundwater systems. Groundwater pump-and-treat systems have often been used to manage cyanide contamination in groundwater. This study examined the feasibility of using in situ precipitation of iron cyanide in a reactive barrier to attenuate the movement of cyanide in groundwater. Laboratory column experiments were performed in which cyanide solutions were passed through mixtures of sand and elemental iron filings. Removal of dissolved cyanide was evaluated in a variety of cyanide-containing influents under various flow rates and sand-to-iron weight ratios. Long-term column tests performed with various cyanide-containing influents under both oxic and anoxic conditions, at neutral pH and at flow rates typical of sand-gravel porous media, yielded effluent concentrations of total cyanide as low as 0.5 mg/L. Effluent cyanide concentrations achieved were close to the solubilities of Turnbull's blue-hydrous ferric oxide solid solutions, indicating co-precipitation of the two solids. Maximum cyanide removal efficiency was achieved with approximately 10% by weight of iron in the sand-iron mixtures; higher iron contents did not increase removal efficiency significantly. Results obtained indicate that in situ precipitation is a promising passive treatment approach for cyanide in groundwater.},
doi = {10.2175/106143096X122456},
journal = {Water Environment Research},
number = 6,
volume = 71,
place = {United States},
year = 1999,
month =
}
  • In situ arsenic removal from groundwater by an iron coating method has great potential to be a cost effective and simple groundwater remediation technique, especially in rural and remote areas where groundwater is used as the main source of drinking water. The in situ arsenic removal technique was first optimized by simulating arsenic removal in various quartz sand columns under anoxic conditions., Its effectiveness was then evaluated in an actual high-arsenic groundwater environment. The mechanism of arsenic removal by the iron coating was investigated under different conditions using scanning electron microscopy (SEM)/X-ray absorption spectroscopy, an electron microprobe, and Fourier transformationmore » infrared spectroscopy. A 4-step alternative cycle aquifer iron coating method was developed. A continuous injection of 5 mmol/L FeSO4 and 2.5 mmol/L NaClO for 96 hours can create a uniform coating of crystalline goethite on the surface of quartz sand in the columns without causing clogging. At a flow rate of 0.45 cm/min of the injection reagents (vi), the time for arsenic (as Na2HAsO4) to pass through the iron-coated quartz sand column was approximately 35 hours, which was much longer than that for tracer fluorescein sodium (approximately 2 hours). The retardation factor of arsenic was 23, and its adsorption capacity was 0.11 mol As per mol Fe, leading to an excellent arsenic removal. In situ arsenic removal from groundwater in an aquifer was achieved by simultaneous injections of As (V) and Fe (II) reagents. When the arsenic content in the groundwater was 233 μg/L, the aqueous phase arsenic was completely removed with an arsenic adsorption of 0.05 mol As per mol Fe. Arsenic fixation resulted from a process of adsorption/co-precipitation, in which arsenic and iron likely formed the arsenic-bearing iron mineral phases with poor crystallinity by way of bidentate binuclear complexes. Thus, the high arsenic removal efficiency of the technique likely resulted from the expanded specific iron oxide/hydroxide surface area with poor crystallinity and from coprecipitation.« less
  • The overall goal of this portion of the project was to package one or more unit processes, as modular components in vertical and/or horizontal recirculation wells, for treatment of volatile organic compounds (VOCs) [e.g., trichloroethene (TCE)] and radionuclides [e.g., technetium (Tc){sup 99}] in groundwater. The project was conceived, in part, because the coexistence of chlorinated hydrocarbons and radionuclides has been identified as the predominant combination of groundwater contamination in the US Department of Energy (DOE) complex. Thus, a major component of the project was the development of modules that provide simultaneous treatment of hydrocarbons and radionuclides. The project objectives included:more » (1) evaluation of horizontal wells for inducing groundwater recirculation, (2) development of below-ground treatment modules for simultaneous removal of VOCs and radionuclides, and (3) demonstration of a coupled system (treatment module with recirculation well) at a DOE field site where both VOCs and radionuclides are present in the groundwater. This report is limited to the innovative treatment aspects of the program. A report on pilot testing of the horizontal recirculation system was the first report of the series (Muck et al. 1996). A comprehensive report that focuses on the engineering, cost and hydrodynamic aspects of the project has also been prepared (Korte et al. 1997a).« less
  • Metal and hydrogen ion acidity and extreme nitrate concentrations at Department of Energy legacy waste sites pose challenges for successful in situ U and Tc bioimmobilization. In this study, we investigated a potential in situ biobarrier configuration designed to neutralize pH and remove nitrate and radionuclides from nitric acid-, U-, and Tc-contaminated groundwater for over 21 months. Ethanol additions to groundwater flowing through native sediment and crushed limestone effectively increased pH (from 4.7 to 6.9), promoted removal of 116 mM nitrate, increased sediment biomass, and immobilized 94% of total U. Increased groundwater pH and significant U removal was also observedmore » in a control column that received no added ethanol. Sequential extraction and XANES analyses showed U in this sediment to be solid-associated U(VI), and EXAFS analysis results were consistent with uranyl orthophosphate (UO2)3(PO4)2·4H2O(s), which may control U solubility in this system. Ratios of respiratory ubiquinones to menaquinones and copies of dissimilatory nitrite reductase genes, nirS and nirK, were at least 1 order of magnitude greater in the ethanol-stimulated system compared to the control, indicating that ethanol addition promoted growth of a largely denitrifying microbial community. Sediment 16S rRNA gene clone libraries showed that Betaproteobacteria were dominant (89%) near the source of influent acidic groundwater, whereas members of Gamma- and Alphaproteobacteria and Bacteroidetes increased along the flow path as pH increased and nitrate concentrations decreased, indicating spatial shifts in community composition as a function of pH and nitrate concentrations. Results of this study support the utility of biobarriers for treating acidic radionuclide- and nitrate-contaminated groundwater.« less
  • A feature article, in Environmental Science and Technology, which describes recent advances in the treatment of chromate contaminated groundwater, with particular emphasis on in situ methods.