Microbial cycling of iron and sulfur in acidic coal mining lake sediments

Lakes caused by coal mining processes are characterized by low pH, low nutrient status, and high concentrations of Fe(II) and sulfate due to the oxidation of pyrite in the surrounding mine tailings. Fe(III) produced during Fe(II) oxidation precipitates to the anoxic acidic sediment, where the microbial reduction of Fe(III) is the dominant electron-accepting process for the oxidation of organic matter, apparently mediated by acidophilic Acidiphilium species. Those bacteria can reduce a great variety of Fe(III)-(hydr)oxides and reduce Fe(III) and oxygen simultaneously which might be due to the small differences in the redox potentials under low pH conditions. Due to the absence of sulfide, Fe(II) formed in the upper 6 cm of the sediment diffuses to oxic zones in the water layer where itcan be reoxidized by Acidithiobacillus species. Thus, acidic conditions are stabilized by the cycling of iron which inhibits fermentative and sulfate-reducing activities. With increasing sediment depth, the amount of reactive iron decrease, the pH increases above 5, and fermentative and as yet unknown Fe(III)-reducing bacteria are also involved in the reduction of Fe(III). Sulfate is reduced apparently by the activity of spore-forming sulfate reducers including new species of Desulfosporosinus that have their pH optimum similar to in situconditions and are not capable of growth at pH 7. However, generation of alkalinity via sulfate reduction is reduced by the anaerobic reoxidation of sulfide back to sulfate. Thus, the microbial cycling of iron at the oxic-anoxic interface and the anaerobic cycling of sulfur maintains environmental conditions appropriate for acidophilic Fe(III)-reducing and acid-tolerant sulfate-reducing microbial communities.     

Spatial Distribution of Geobacteraceae and Sulfate‐Reducing Bacteria During In Situ Bioremediation of Uranium‐Contaminated Groundwater

Analysis of the physiological status of subsurface microbial communities generally relies on the study of unattached microorganisms in the groundwater. These approaches have been employed in studies on bioremediation of uranium‐contaminated groundwater at a study site in Rifle, Colorado, in which Geobacter species typically account for over 90 percent of the microbial community in the groundwater during active uranium reduction. However, to develop efficient in situ bioremediation strategies it is necessary to know the status of sediment‐associated microorganisms as well. In order to evaluate the distribution of the natural community of Geobacter during bioremediation of uranium, subsurface sediments were packed into either passive flux meters (PFMs) or sediment columns deployed in groundwater monitoring wells prior to acetate injection during in situ biostimulation field trials. The trials were performed at the Department of Energy's (DOE's) Rifle Integrated Field Research Challenge site. Sediment samples were removed either during the peak of Fe(III) reduction or the peak of sulfate reduction over the course of two separate field experiments and preserved for microscopy. Direct cell counts using fluorescence in situ hybridization (FISH) probes targeting Geobacter species indicated that the majority of Geobacter cells were unattached during Fe(III) reduction, which typically tracks with elevated rates of uranium reduction. Similar measurements conducted during the sulfate‐reducing phase revealed the majority of Geobacter to be attached following exhaustion of more readily bioavailable forms of iron minerals. Laboratory sediment column studies confirmed observations made with sediment samples collected during field trials and indicated that during Fe(III) reduction, Geobacter species are primarily unattached (90 percent), whereas the majority of sulfate‐reducing bacteria and Geobacter species are attached to sediment surfaces when sulfate reduction is the predominant form of metabolism (75 percent and 77 percent, respectively). In addition, artificial sediment experiments showed that pure cultures of Geobacter uraniireducens, isolated from the Rifle site, were primarily unattached once Fe(III) became scarce. These results demonstrate that, although Geobacter species must directly contact Fe(III) oxides in order to reduce them, cells do not firmly attach to the sediments, which is likely an adaptive response to sparsely and heterogeneously dispersed Fe(III) minerals in the subsurface. © 2013 Wiley Periodicals, Inc.     

Potential Remobilization of Toxic Anions during Reduction of Arsenated and Chromated Schwertmannite by the Dissimilatory Fe(III)-Reducing Bacterium Acidiphilium cryptum JF-5

Schwertmannite, an iron(III)-oxyhydroxysulfate formed in acidic mining-impacted stream or lake waters often contaminated with toxic elements like arsenate or chromate, is able to incorporate high amounts of these oxyanions. Detoxification of the water might be achieved if precipitated arsenated or chromated schwertmannite is fixed in the sediment. However, under reduced conditions, reductive dissolution of iron oxides mediated by the activity of Fe(III)-reducing bacteria might mobilize arsenate and chromate again. In this study, the reduction of synthesized arsenated or chromated schwertmannite by the acidophilic Fe(III)-reducer Acidiphilium cryptum JF-5, isolated from an acidic mining-impacted sediment, was investigated. In TSB medium at pH 2.7 with glucose as electron donor, A. cryptum JF-5 reduced about 10% of the total Fe(III) present in pure synthetic schwertmannite but only 5% of Fe(III) present in arsenated schwertmannite. In contrast to sulfate that was released during the reductive dissolution of pure schwertmannite, arsenate was not released during the reduction of arsenated schwertmannite probably due to the high surface complexation constant of arsenate and Fe(III). In medium containing chromated schwertmannite, no Fe(II) was formed, and no glucose was consumed indicating that chromate might have been toxic to cells of A. cryptum JF-5. Both As(V) or Cr(VI) could not be utilized as electron acceptor by A. cryptum JF-5. A comparison between autoclaved (121 °C for 20 min) and non-autoclaved schwertmannite samples demonstrated that nearly 100%of the bound sulfate was released during heating, and FTIR spectra indicated a transformation of schwertmannite to goethite. This structural change was not observed with autoclaved arsenated or chromated schwertmannite. These results suggest that the mobility of arsenate and chromate is not enhanced by the activity of acidophilic Fe(III)-reducing bacteria in mining-impacted sediments. In contrast, the presence of bound arsenate and chromate seemed to stabilize schwertmannite against reductive dissolution and its further transformation to goethite that is an ongoing process in those sediments.     

Functions of Straw for In Situ Remediation of Acidic Mining Lakes

The addition of straw in combination with Carbokalk, a by-product from the sugar-industry, was successfully used to stimulate microbial alkalinity generation in an acidic mining lake. To get detailed information about functions of straw, anenclosure experiment was carried out. Straw bundles were placedat the sediment surface of an acidic mining lake (ML 111) and thephysiochemical conditions and the microbiology of the sediment-water contact zone were studied. Straw was degraded by anaerobic microorganisms and dissolved organic carbon (DOC) leached from straw bundles. Pigmented flagellates responded to the DOC supply in the water column anda considerable amount of algal carbon was transported to the sediment. Straw addition led to microbial reduction of iron andsulfate in the sediment. Sulfate reduction was observed at a pHof 5.5. The pH, however, was not high enough to precipitate H₂S completely. Thus, some H₂S diffused into the watercolumn, where it was reoxidized. Straw did not create orstabilize an anoxic water body above the sediment. Microbial sulfate reduction and pyrite formation only took place in the sediment,whereas iron reduction also took place in the straw. Straw, however, altered the flow conditions above the sediment surfaceand prevented complete mixing of the profundal water. Straw didnot serve as a substratum for a reactive biofilm. We conclude that the most important function of straw for mining lake remediation is to be a long-term nutrient source for microbialalkalinity generation in the sediment.     

Accumulation of dechlorination daughter products: A valid metric of chloroethene biodegradation

In situ reductive dechlorination of perchloroethene (PCE) and trichloroethene (TCE) generates characteristic chlorinated (cis‐dichloroethene [cis‐DCE] and vinyl chloride [VC]) and nonchlorinated (ethene and ethane) products. The accumulation of these daughter products is commonly used as a metric for ongoing biodegradation at field sites. However, this interpretation assumes that reductive dechlorination is the only chloroethene degradation process of any significance in situ and that the characteristic daughter products of chloroethene reductive dechlorination persist in the environment. Laboratory microcosms, prepared with aquifer and surface‐water sediments from hydrologically diverse sites throughout the United States and amended with [1,2‐¹⁴C] TCE, [1,2‐¹⁴C] DCE, [1,2‐¹⁴C] DCA, or [1,2‐¹⁴C] VC, demonstrated widely variable patterns of intermediate and final product accumulation. In predominantly methanogenic sediment treatments, accumulation of ¹⁴C‐DCE, ¹⁴C‐VC, ¹⁴C‐ethene, and ¹⁴C‐ethane predominated. Treatments characterized by significant Fe(III) and/or Mn(IV) reduction, on the other hand, demonstrated substantial, and in some cases exclusive, accumulation of ¹⁴CO₂ and ¹⁴CH₄. These results suggest that relying on the accumulation of cis‐DCE, VC, ethene, and ethane may substantially underestimate overall chloroethene biodegradation at many sites. © 2007 Wiley Periodicals, Inc. *

1 This article is a U.S. government work and, as such, is in the public domain in the United States of America.

     

Geochemistry of Iron and Sulfur in the Zone of Microbial Sulfate Reduction in Mine Tailings

The cycling of iron and sulfur in mine tailings depends on various chemical and microbial reactions. The present study was undertaken in order to assess the role played by populations of sulfate-reducing bacteria (SRB) on the fate of Fe and SO₄ ^2- in Cu–Zn and Au tailings. Samples were taken along a 50-cm deep profile at all sites and analyzed for SRB populations, solid-phase mineralogy and porewater geochemistry. Results indicated that the Cu–Zn tailings were highly oxidized near the surface, as shown by the very low pH, high redox potential, large concentrations of soluble Cu, Zn and sulfate in the porewaters, and the depletion of pyrite. On the other hand, Au tailings were more pH neutral, slightly anoxic, and showed low concentrations of Fe and SO₄ ^2- in the porewaters and very little pyrite oxidation. SRB populations in the Cu–Zn tailings increased with depth, just below the oxic/anoxic interface and were linked to a decline of sulfate and DOC concentrations around the same depths. However, large concentrations of dissolved Fe were also observed around the same depth intervals. Our results suggest that SRB could be involved in sulfate reduction in the Cu–Zn tailings, because the solubility of sulfate was not controlled by the precipitation of sulfate-rich minerals. However, the presence of soluble Fe in the reduced portion of the tailings was also indicative of the presence of iron reducing bacteria (IRB). These bacteria were not enumerated in the present study, but their co-occurrence with SRB has been reported in the past in similar mining environments. The decline of sulfate and the release of soluble iron into the porewaters were also paralleled by a pH increase and the generation of alkalinity. In the Au tailings, SRB populations were generally constant throughout the depth profile and could not be ascribed to sulfate reduction in the porewaters. The solubilities of sulfate and iron in these tailings were partially controlled by jarosite and Fe-oxide minerals. It is then clear that SRB populations could be recovered from various mining sites, but their activity cannot be ascertained based on microbial enumeration and geochemical data.     

Enhancement of arsenic mobility by Fe(III)-reducing bacteria from iron oxide minerals

Batch bioleaching experiments were conducted using the Fe(III)-reducing bacteria, Shewanella putrefaciens CN32, to determine the effect of the Fe(III) reduction on As mobilization. For this purpose, Fe(III) reduction experiments were also performed to deduce the optimum conditions of the bioleaching experiment. In the Fe(III) reduction experiment, insoluble Fe(III), such as synthesized poorly and well crystalline hydrous ferric oxide (HFO), was rarely used as electron acceptor by S. putrefaciens. However, the addition of a humic substance (2,6-anthraquinone disulfonate, AQDS) greatly increased iron reduction capacity (5–10 times) under the same conditions. For the poorly and well crystalline HFO, the effective carbon sources as electron donor were acetate and lactate, respectively. In bioleaching experiments using the two types of synthesized Fe(III) oxide minerals bearing As (poorly crystalline HFO and well crystalline HFO), S. putrefaciens enhanced the As mobilization, with 1,870 and 1,460 mg kg^?1 of As released in the poorly and well crystalline HFO, respectively. From a correlation coefficient analysis between reduced Fe and released As, the R ² values were 0.8612 and 0.9115, respectively. These results indicated that the reduction of Fe(III) can enhance the As mobilization. Therefore, bioleaching using the Fe(III)-reducing mechanism can be useful for remediation of As contaminated soil.     

Assessment of the Ecological Integrity of Traunsee (Austria) Via Analysis of Sediments and Benthic Microbial Communities

Since nearly one hundred years Traunsee experiences the import of tons of liquid and solid waste originating from salt and soda production. Today, the lake exhibits chloride concentrations of up to 170 mg L^-1 and 19% of the lake floor are directly or indirectly influenced by industrial deposits (ID). Based on the comparison of several microbial parameters in unaffected, directly affected and intermediate lake bottom sediments, the ecological integrity of the lake was evaluated. The highly alkaline ID, which were exclusively colonized by microorganisms, harbored a bacterial community reduced by a factor of 10 in abundance and biomass compared to undisturbed sediment areas within the lake. The bacterial community of ID was furthermore characterized by a reduced content of actively respiring cells (INT-formazan reduction), a lower frequency of dividing cells (FDC) and a significantly reduced cell and biomass production. A 80 to 90% reduction in carbon recycling is estimated for the area exclusively covered by ID. Protists, although occasionally absent from the industrial sediments, were in general found to be less sensitive to the contaminant stress. Differences in alkalinity and dissolved organic carbon (DOC) concentrations of sediment porewaters as well as the total organic content and C/N ratios of sediments partly explain the microbial pattern observed at the various sampling sites. Possible consequences of the continuous industrial tailings for the whole lake ecosystem and the validation of the ecological integrity are discussed.     

Role of iron chemistry in controlling the release of pollutants from resuspended sediments

Aquatic sediments often contain a large number of chemical contaminants that are potential pollutants. It is often presumed that such contaminants are released to the water column during sediment resuspension and, in there, adversely impact aquatic life and other beneficial uses of the water. However, extensive laboratory and field studies of about 100 contaminated sediments from across the United States that specifically addressed this type of release showed that of about 30 common heavy metals, organic compounds, and other potential pollutants, only manganese II and ammonia were released to then remain in the water column after sediment resuspension. These results indicated that the chemistry of aqueous iron controls the availability of many contaminants in resuspended sediment. The formation of ferric hydroxide during sediment suspension into the water column, as a result of the reaction between ferrous iron in the sediments and dissolved oxygen in the water column, leads to rapid scavenging of many contaminants in the Fe(OH)₃ precipitate. The scavenged contaminants are redeposited in the sediments. This article reviews the role of the aqueous chemistry of iron as it relates to controlling the release of potential pollutants from resuspended sediments. © 2005 Wiley Periodicals, Inc.     

Chemical Oxidation Performance in High Temperature,Saline Groundwater Impacted With Hydrocarbons

A series of laboratory microcosm experiments and a field pilot test were performed to evaluate the potential for in situ chemical oxidation (ISCO) of aromatic hydrocarbons and methyl tertiary butyl ether (MTBE), a common oxygenate additive in gasoline, in saline, high temperature (more than 30 °C) groundwater. Groundwater samples from a site in Saudi Arabia were amended in the laboratory portion of the study with the chemical oxidants, sodium persulfate (Na₂S₂O₈) and sodium percarbonate (Na₂(CO₃)₂), to evaluate the changes in select hydrocarbon and MTBE concentrations with time. Almost complete degradation of the aromatic hydrocarbons, naphthalene and trimethylbenzenes (TMBs), was found in the groundwater sample amended with persulfate, whereas the percarbonate‐amended sample showed little to no degradation of the target hydrocarbon compounds in the laboratory. Isotopic analyses of the persulfate‐amended samples suggested that C‐isotope fractionation for xylenes occurred after approximately 30 percent reduction in concentration with a decline of about 1 percent in the δ¹³C values of xylenes. Based on the laboratory results, pilot‐scale testing at the Saudi Arabian field site was carried out to evaluate the effectiveness of chemical oxidation using nonactivated persulfate on a high temperature, saline petroleum hydrocarbon plume. Approximately 1,750 kg of Na₂S₂O₈ was delivered to the subsurface using a series of injection wells over three injection events. Results obtained from the pilot test indicated that all the target compounds decreased with removal percentages varying between 86 percent for naphthalene and more than 99 percent for the MTBE and TMBs. The benzene, toluene, ethylbenzene, and xylene compounds decreased to 98 percent on average. Examination of the microbial population upgradient and downgradient of the ISCO reactive zone suggested that a bacteria population was present following the ISCO injections with sulfate‐reducing bacteria (SRB) being the dominant bacteria present. Measurements of inorganic parameters during injection and postinjection indicated that the pH of the groundwater remained neutral following injections, whereas the oxidation–reduction potential remained anaerobic throughout the injection zone with time. Nitrate concentrations decreased within the injection zone, suggesting that the nitrate may have been consumed by denitrification reactions, whereas sulfate concentrations increased as expected within the reactive zone, suggesting that the persulfate produced sulfate. Overall, the injection of the oxidant persulfate was shown to be an effective approach to treat dissolved aromatic and associated hydrocarbons within the groundwater. In addition, the generation of sulfate as a byproduct was an added benefit, as the sulfate could be utilized by SRBs present within the subsurface to further biodegrade any remaining hydrocarbons. ©2015 Wiley Periodicals, Inc.     

The effect of sediment redox chemistry on solubility/chemically active forms of selected metals in bottom sediment receiving produced water discharge

The effect of sediment redox conditions on the solubility behavior of Fe, Pb, Ni, Ba, and Cu in bottom sediment collected from a produce water discharge site was investigated using kinetics and chemical fractionation procedures. Sediment collected was composited and subsamples incubated in laboratory microcosms under controlled Eh-pH conditions. Sediment was sequentially extracted for determining metals in five fractions (exchangeable, carbonate, bound to iron and manganese oxide, bound to organic matter and sulfide, mineral matrix or residue). Metal distribution in the fractions indicates that under oxidizing sediment conditions, the behavior of Fe, Pb and Ni were governed by Fe(III) and Mn(IV) oxides; Ba by insoluble complexation with humic compounds; and Cu by carbonates and humic complexation. Under reducing sediment condition, the behaviors of Fe and Cu were controlled by the formation of insoluble sulfides and humic complexes; the behaviors of Ni and Ba by carbonate and Pb behavior by sulfides, carbonates and humic complexes. With increases in sediment redox potential, the affinity between Fe(III), Mn(IV) oxides and Fe, Pb, Ni, Cu increased, the affinity between insoluble large molecular humic and Ba increased, and the affinity between carbonates and Cu increased. With decreasing sediment redox potential, the affinity between carbonates and Fe, Ni, Ba increased; the affinity between sulfides, humic substances and Fe, Pb, Ni, Cu also increased. Upon Fe(III) oxide reduction, it is estimated that 20% of total reducible Fe(III) oxides was reduced by direct bacterial reduction (K = −42.6 ppm/day), 80% of total reducible Fe(III) oxides was associated with chemical fractions attributed to sulfide oxidation (K = −171.5 ppm/day). The rate constants (ppm/day) for dissolved Ni (Eh <0 mV), Pb (Eh < −80 mV) and Cu (−80 mV < Eh <0 mV) are −1.6, −0.047 and −0.16, respectively. In our incubation period, the rate constants (ppm/day) for Ni bound to Fe(III) and Mn(IV) oxides, Ba bound to carbonates and Cu bound to insoluble large molecular humic are −3.2, 0.91 and 4.3, respectively.     

Bacterioplankton Community Structure and Dynamics in Enclosures During Bioremediation Experiments in an Acid Mining Lake

In an acid mining lake (pH 2.6) enclosure experiments wereperformed with the addition of different concentrations oforganic carbon, nitrogen and phosphorus. SSCP-communityfingerprints, based on 16S rRNA gene amplicons, were performed tomonitor changes in the structure of the total bacterialcommunity and the sulfate reducing bacteria (SRB) in themesocosms. Total bacterial cell counts, as assessed byepifluorescence microscopy, were increased in the mesocosmsamended with organic carbon. The addition of carbon alsoincreased the number of abundant bacterial taxa substantiallyalong depth. Sulfate reducing bacteria (SRB) could be detected inall enclosures and all parts of the water column. These SRBbelonged to genus Desulfobacter as indicated bycoroborating molecular data.     

Acidification Trends and the Evolution of Neutralization Mechanisms through Time at the Bear Brook Watershed in Maine (BBWM), U.S.A.

The paired catchment study at the forested Bear Brook Watershed in Maine (BBWM) U.S.A. documents interactions among short- to long-term processes of acidification. In 1987–1989, runoff from the two catchments was nearly identical in quality and quantity. Ammonium sulfate has been added bi-monthly since 1989 to the West Bear catchment at 1800 eq ha^-1 a^-1; the East Bear reference catchment is responding to ambient conditions. Initially, the two catchments had nearly identical chemistry (e.g., Ca²⁺, Mg²⁺, SO₄ ^2-, and alkalinity ≈82, 32, 100, and 5 μeq L^-1, respectively). The manipulated catchment responded initially with increased export of base cations, lower pH and alkalinity, and increased dissolved Al,NO₃ ^- and SO₄ ^2-. Dissolved organic carbon and Si have remained relatively constant. After 7 yr of treatment, the chemical response of runoff switched to declining base cations, with the other analytes continuing their trends; the exports of dissolved and particulate Al, Fe, and P increased substantially as base cations declined. The reference catchment has slowly acidified under ambient conditions, caused by the base cation supply decreasing faster than the decrease of SO₄ ², as pollution abates. Export of Al, Fe and, P is mimicking that of the manipulated watershed, but is lower in magnitude and lags in time. Probable increasing SO₄ ^2- adsorption caused by acidification has moderated the longer-term trends of acidification of both watersheds. The trends of decreasing base cations were interrupted by the effects of several short-term events, including severe ice storm damage to the canopy, unusual snow pack conditions, snow melt and rain storms, and episodic input of marine aerosols. These episodic events alter alkalinity by5 to 15 μeq L^-1 and make it more difficult to determine recovery from pollution abatement.     

Managing compost stability and amendment to soil to enhance soil heating during soil solarization

Soil solarization is a method of soil heating used to eradicate plant pathogens and weeds that involves passive solar heating of moist soil mulched (covered) with clear plastic tarp. Various types of organic matter may be incorporated into soil prior to solarization to increase biocidal activity of the treatment process. Microbial activity associated with the decomposition of soil organic matter may increase temperatures during solarization, potentially enhancing solarization efficacy. However, the level of organic matter decomposition (stability) necessary for increasing soil temperature is not well characterized, nor is it known if various amendments render the soil phytotoxic to crops following solarization. Laboratory studies and a field trial were performed to determine heat generation in soil amended with compost during solarization. Respiration was measured in amended soil samples prior to and following solarization as a function of soil depth. Additionally, phytotoxicity was estimated through measurement of germination and early growth of lettuce seedlings in greenhouse assays. Amendment of soil with 10% (g/g) compost containing 16.9 mg CO₂/g dry weight organic carbon resulted in soil temperatures that were 2–4 °C higher than soil alone. Approximately 85% of total organic carbon within the amended soil was exhausted during 22 days of solarization. There was no significant difference in residual respiration with soil depth down to 17.4 cm. Although freshly amended soil proved highly inhibitory to lettuce seed germination and seedling growth, phytotoxicity was not detected in solarized amended soil after 22 days of field solarization.     

A Biogeochemical Comparison of Two Well-Buffered Catchments with Contrasting Histories of Acid Deposition

Much of the biogeochemical cycling research in catchments in the past 25 years has been driven by acid deposition research funding. This research has focused on vulnerable base-poor systems; catchments on alkaline lithologies have received little attention. In regions of high acid loadings, however, even well-buffered catchments are susceptible to forest decline and episodes of low alkalinity in streamwater. As part of a collaboration between the Czech and U.S. Geological Surveys, we compared biogeochemical patterns in two well-studied, well-buffered catchments: Pluhuv Bor in the western Czech Republic, which has received high loading of atmospheric acidity, and Sleepers River Research Watershed in Vermont, U.S.A., where acid loading has been considerably less. Despite differences in lithology, wetness, forest type, and glacial history, the catchments displayed similar patterns of solute concentrations and flow. At both catchments, base cation and alkalinity diluted with increasing flow, whereas nitrate and dissolved organic carbon increased with increasing flow. Sulfate diluted with increasing flow at Sleepers River, while at Pluhuv Bor the sulfate-flow relation shifted from positive to negative as atmospheric sulfur (S) loadings decreased and soil S pools were depleted during the 1990s. At high flow, alkalinity decreased to near 100 μeq L^-1 at Pluhuv Bor compared to 400 μeq L^-1 at Sleepers River. Despite the large amounts of S flushed from Pluhuv Bor soils, these alkalinity declines were caused solely by dilution, which was greater at Pluhuv Bor relative to Sleepers River due to greater contributions from shallow flow paths at high flow. Although the historical high S loading at Pluhuv Bor has caused soil acidification and possible forest damage, it has had little effect on the acid/base status of streamwater in this well-buffered catchment.     

Investigating the Use of Iron Reducing Bacteria for the Removal of Arsenic from Contaminated Soils

Clean-up techniques, which were developed for removing cationic heavy metals from contaminated soils, are inappropriate for the metalloid As, which is a common and highly toxic pollutant. Because arsenic is mainly found associated with the hydrous ferric oxides of the soil, a possible mechanism for the mobilisation of this element is the reductive dissolution of Fe(III) oxyhydroxides. In this paper we investigate the possibility to mobilise arsenic, using the Fe(III)-reducing bacterium Desulfuromonas Palmitatis. The initial experiments were carried out using a crystalline ferric arsenate as model compound, i.e. scorodite (FeAsO₄.2H₂O). D. palmitatis was found able to reduce the trivalent iron of scorodite at a percentage of 80% within 16 days, but arsenic remained in the pentavalent state, and reprecipitated with Fe(II) in the form of low solubility ferrous arsenates. To avoid the precipitation of ferrous arsenates the subsequent experiments with soil were conducted by combining the reducing ability of D. palmitatis with the chelating strength of EDTA (ethylenediamine tetracetic acid), which can form strong aqueous complexes with Fe(II). Approximately 60% of Fe and 75% of As were recovered in the aqueous solution in the presence of EDTA, while in the simple biological treatment no Fe was dissolved and only a 3% of As was mobilised.     

Phosphogypsum chemistry under highly anoxic conditions

Phosphogypsum (PG), primary byproduct from phosphoric acid production, is accumulated in large stockpiles and occupies vast areas of land. Contaminants emanating from PG stacks can impact the environment including waterbodies. The major constraint for PG use in the environment is the presence of metals in high concentrations. Reduction of sulfate found in PG and significance of sulfide production in reducing aqueous concentrations of toxic metals were studied. Mississippi River alluvial sediment amended with PG was equilibrated under controlled redox (-250 mV) and pH (5.5, 6.5, and 7.5) conditions. Phosphogypsum addition resulted in a large increase in sulfide levels in sediment suspensions. As a result, the solubility of spiked heavy metals (Cd and Cr, 100 and 1000 mg kg(-1)) and natural trace elements (As, Ba, and Cd) was significantly reduced by precipitation as insoluble sulfides. Sediment pH also influenced sulfate reduction and sulfide formation in both PG-amended and control sediment. Low sediment pH (5.5) resulted in the highest release of all studied metals and sulfate into sediment solution. This study indicates that if PG or PG-products are placed in neutral to alkaline sediments/soils and/or reducing environments, metals released at toxic levels should be of little concern to the wetland environment.     

Distribution of Redox-sensitive Elements in Bottom Waters,Porewaters and Sediments of Rogoznica Lake (Croatia) in Both Oxic and Anoxic Conditions

Geochemical, mineralogical and sedimentological analyses were carried out to contrast two different sites (respectively characterized by permanently oxic and anoxic conditions) in a small, meromictic, seawater lake. In fact, due to relatively high organic matter content, and reduced water exchange, the Rogoznica Lake has almost permanent anoxic conditions below the depth of 12 m, where sediment can be considered an anoxic–sulphidic sedimentary environment. Different water column and sediments redox conditions affect the distribution and speciation of major redox-sensitive metals (Fe, Mn, Mo), reduced sulphur species (RSS) and dissolved organic C (DOC). Trace metals, especially those that accumulate in anoxic–sulphidic environments (Fe, Mo) showed a marked enrichment in the solid phase, whereas the low solubility of sulphides leads to low porewater concentrations. The relatively high sedimentary enrichment of Mo (up to 81 mg/kg) also confirms highly anoxic conditions within the Rogoznica Lake sediments. Results clearly show that chemical species within the sediments will tend towards equilibrium between porewater and solid phase according the prevailing environment conditions such as redox, pH, salinity, DOC.     

Stabilization of As, Cr, Cu, Pb and Zn in soil using amendments--a review

The spread of contaminants in soil can be hindered by the soil stabilization technique. Contaminant immobilizing amendments decrease trace element leaching and their bioavailability by inducing various sorption processes: adsorption to mineral surfaces, formation of stable complexes with organic ligands, surface precipitation and ion exchange. Precipitation as salts and co-precipitation can also contribute to reducing contaminant mobility. The technique can be used in in situ and ex situ applications to reclaim and re-vegetate industrially devastated areas and mine-spoils, improve soil quality and reduce contaminant mobility by stabilizing agents and a beneficial use of industrial by-products. This study is an overview of data published during the last five years on the immobilization of one metalloid, As, and four heavy metals, Cr, Cu, Pb and Zn, in soils. The most extensively studied amendments for As immobilization are Fe containing materials. The immobilization of As occurs through adsorption on Fe oxides by replacing the surface hydroxyl groups with the As ions, as well as by the formation of amorphous Fe(III) arsenates and/or insoluble secondary oxidation minerals. Cr stabilization mainly deals with Cr reduction from its toxic and mobile hexavalent form Cr(VI) to stable in natural environments Cr(III). The reduction is accelerated in soil by the presence of organic matter and divalent iron. Clays, carbonates, phosphates and Fe oxides were the common amendments tested for Cu immobilization. The suggested mechanisms of Cu retention were precipitation of Cu carbonates and oxy-hydroxides, ion exchange and formation of ternary cation-anion complexes on the surface of Fe and Al oxy-hydroxides. Most of the studies on Pb stabilization were performed using various phosphorus-containing amendments, which reduce the Pb mobility by ionic exchange and precipitation of pyromorphite-type minerals. Zn can be successfully immobilized in soil by phosphorus amendments and clays.     

Field application of palladized iron for the dechlorination of trichloroethene

Palladized iron (Pd/Fe) has been tested under field conditions for the dechlorination of trichloroethene (TCE) in groundwater. Contaminated water was pumped from aquifers in Ohio (0.7– 1.5 mg/l TCE) and Missouri (2–9 mg/l TCE and 1,2-dichloroethene) and passed through columns of Pd/Fe. The experiments demonstrated that the dechlorination reaction occurs efficiently until the surface of the Pd/Fe becomes fouled. Regeneration of the surface with dilute (1M) hydrochloric acid is easily accomplished under laboratory conditions, but initially was unsuccessful in the field. Further experiments indicated, that reduced sulfur species, although not naturally present in the groundwater being treated, were permanently poisoning the palladium. Apparently, sulfur-reducing bacteria utilize the hydrogen produced by the Pd/Fe process and reduce the sulfate that is present. An anion exchange column was used to remove sulfate (20 mg/l) from groundwater at the Kansas City Plant in order to test this theory. Under these conditions, a column of Pd/Fe was repetitively regenerated for a 4-week period. A second column, not protected by sulfate removal, could not be regenerated. The results demonstrated that Pd/Fe could be used in a long-term field process if a material with more resistance to Fe and Pd losses is developed.