Impact of sample preparation on mineralogical analysis of zero-valent iron reactive barrier materials

Permeable reactive barriers (PRBs) of zero-valent iron (Fe(0)) are increasingly being used to remediate contaminated ground water. Corrosion of Fe(0) filings and the formation of precipitates can occur when the PRB material comes in contact with ground water and may reduce the lifespan and effectiveness of the barrier. At present, there are no routine procedures for preparing and analyzing the mineral precipitates from Fe(0) PRB material. These procedures are needed because mineralogical composition of corrosion products used to interpret the barrier processes can change with iron oxidation and sample preparation. The objectives of this study were (i) to investigate a method of preparing Fe(0) reactive barrier material for mineralogical analysis by X-ray diffraction (XRD), and (ii) to identify Fe mineral phases and rates of transformations induced by different mineralogical preparation techniques. Materials from an in situ Fe(0) PRB were collected by undisturbed coring and processed for XRD analysis after different times since sampling for three size fractions and by various drying treatments. We found that whole-sample preparation for analysis was necessary because mineral precipitates occurred within the PRB material in different size fractions of the samples. Green rusts quickly disappeared from acetone-dried samples and were not present in air-dried and oven-dried samples. Maghemite/magnetite content increased over time and in oven-dried samples, especially after heating to 105 degrees C. We conclude that care must be taken during sample preparation of Fe(0) PRB material, especially for detection of green rusts, to ensure accurate identification of minerals present within the barrier system.     

Analysis and performance of oil well cement with 30 years of CO2 exposure from the SACROC Unit,West Texas,USA

A core sample including casing, cement, and shale caprock was obtained from a 30-year old CO₂-flooding operation at the SACROC Unit, located in West Texas. The core was investigated as part of a program to evaluate the integrity of Portland-cement based wellbore systems in CO₂-sequestration environments. The recovered cement had air permeabilities in the tenth of a milliDarcy range and thus retained its capacity to prevent significant flow of CO₂. There was evidence, however, for CO₂ migration along both the casing–cement and cement–shale interfaces. A 0.1–0.3 cm thick carbonate precipitate occurs adjacent to the casing. The CO₂ producing this deposit may have traveled up the casing wall or may have infiltrated through the casing threads or points of corrosion. The cement in contact with the shale (0.1–1 cm thick) was heavily carbonated to an assemblage of calcite, aragonite, vaterite, and amorphous alumino-silica residue and was transformed to a distinctive orange color. The CO₂ causing this reaction originated by migration along the cement–shale interface where the presence of shale fragments (filter cake) may have provided a fluid pathway. The integrity of the casing–cement and cement–shale interfaces appears to be the most important issue in the performance of wellbore systems in a CO₂ sequestration reservoir.     

Metolachlor dechlorination by zerovalent iron during unsaturated transport

Permeable zerovalent iron (Fe0) barriers have become an established technology for remediating contaminated ground water. This same technology may be applicable for treating pesticides amenable to dehalogenation as they move downward in the vadose zone. By conducting miscible displacement experiments in the laboratory with metolachlor [2-chloro-N-(2-ethyl-6-methylphenyl)-N-(2-methoxy-1-methylethyl)acetamide; a chloroacetanilide herbicide] under unsaturated flow, we provide proof-of-concept for such an approach. Transport experiments were conducted in repacked, unsaturated soil columns attached to vacuum chambers and run under constant matrix potential (-30 kPa) and Darcy flux (approximately 2 cm d(-1)). Treatments included soil columns equipped with and without a permeable reactive barrier (PRB) consisting of a Fe0-sand (50:50) mixture supplemented with Al2(SO4)3. A continuous pulse of 14C-labeled metolachlor (1.45 mM) and tritiated water (3H2O) was applied to top of the columns for 10 d. Results indicated complete (100%) metolachlor destruction, with the dehalogenated product observed as the primary degradate in the leachate. Similar results were obtained with a 25:75 Fe0-sand barrier but metolachlor destruction was not as efficient when unannealed iron was used or Al2(SO4)3 was omitted from the barrier. A second set of transport experiments used metolachlor-contaminated soil in lieu of a 14C-metolachlor pulse. Under these conditions, the iron barrier decreased metolachlor concentration in the leachate by approximately 50%. These results provide initial evidence that permeable iron barriers can effectively reduce metolachlor leaching under unsaturated flow.     

Enhancing metolachlor destruction rates with aluminum and iron salts during zerovalent iron treatment

Pesticide-contaminated soil may require remediation to mitigate ground and surface water contamination. We determined the effectiveness of zerovalent iron (Fe(0)) to dechlorinate metolachlor [2-chloro-N-(2-ethyl-6-methylphenyl)-N-(2-methoxy-1-methyl ethyl) acetamide] in the presence of aluminum and iron salts. By treating aqueous solutions of metolachlor with Fe(0), we found destruction kinetics were greatly enhanced when Al, Fe(II), or Fe(II) salts were added, with the following order of destruction kinetics observed: Al2(SO4)3 > AlCl3 > Fe2(SO4)3 > FeCl3. A common observation was the formation of green rusts, mixed Fe(II)-Fe(III) hydroxides with interlayer anions that impart a greenish-blue color. Central to the mechanism responsible for enhanced metolachlor loss may be the role these salts play in facilitating Fe(II) release. By tracking Al and Fe(II) in a Fe(0) + Al2(SO4)3 treatment of metolachlor, we observed that Al was readily sorbed by the corroding iron with a corresponding release of Fe(II). The manufacturing process used to produce the Fe(0) also profoundly affected destruction rates. Metolachlor destruction rates with salt-amended Fe(0) were greater with annealed iron (indirectly heated under a reducing atmosphere) than unannealed iron. Moreover, the optimum pH for metolachlor dechlorination in water and soil differed between iron sources (pH 3 for unannealed, pH 5 for annealed). Our results indicate that metolachlor destruction by Fe(0) treatment may be enhanced by adding Fe or Al salts and creating pH and redox conditions favoring the formation of green rusts.     

Characterization of iron- and manganese-cemented redoximorphic aggregates in wetland soils contaminated with mine wastes

In wetlands, translocation of Fe and Mn from reducing to oxidizing zones creates localized enrichments and depletions of oxide minerals. In zones of enrichment, oxides cement matrix particles together into aggregates. In this paper, we describe the various Fe- and Mn-cemented features present in the 1 to 2-mm size fraction of mine-waste contaminated wetland soils of the Coeur d'Alene (CDA) River Basin in northern Idaho. These aggregates are categorized based on color and morphology. Total Fe and Mn concentrations are also reported. Distribution of the aggregates in soil profiles along an elevation transect with varying water table heights was investigated. Six distinct categories of aggregates were characterized in the 1 to 2-mm size fraction. The two most predominant categories were aggregates cemented by only Fe oxides and aggregates cemented by a mixture of Fe and Mn oxides. Iron-depleted aggregates, Fe and Mn-cemented sand aggregates, and root channel linings were also identified. The remaining aggregates were categorized into a catch-all category that consisted of primarily charcoal particles. The highest Fe content was in the root channel linings, and the highest Mn content was in the Fe/Mn cemented particles. Iron-cemented aggregates were most common in surface horizons at all sites, and root channels were most common in the 30 to 45-cm core at the lowland point, reflecting the presence of deep rooting vegetation at this site. Spatial distributions of other aggregates at the site were not significant.     

Passive treatment of acid mine drainage with high metal concentrations using dispersed alkaline substrate

Passive treatment systems based on the dissolution of coarse calcite grains are widely used to remediate acid mine drainage (AMD). Unfortunately, they tolerate only low metal concentrations or acidity loads, because they are prone to passivation (loss of reactivity due to coating) and/or clogging (loss of permeability) by precipitates. To overcome these problems, a dispersed alkaline substrate (DAS) composed of a fine-grained alkaline reagent (calcite sand) mixed with a coarse inert matrix (wood chips) was developed. The small grains provide a large reactive surface and dissolve almost completely before the growing layer of precipitates passivates the substrate, whereas the dispersion of nuclei for precipitation on the inert surfaces retards clogging. Chemical and hydraulic performance of DAS was investigated in two laboratory columns fed at different flow rates with natural AMD of pH 2.3 to 3.5 and inflow net acidity 1350 to 2300 mg/L as CaCO(3). The DAS columns removed 900 to 1600 mg/L net acidity, 3 to 4.5 times more than conventional passive treatment systems. Regardless of the flow rate employed, Al, Fe(III), Cu, and Pb were virtually eliminated. Minor Zn, Ni, and Cd were removed at low flow rates. High acidity removal is possible because these metals accumulate intentionally in DAS, and their precipitation promotes further calcite dissolution. During 15 mo, DAS operated without clogging at 120 g acidity/m(2).d, four times the loading rate recommended for conventional passive systems; DAS may therefore be capable of treating AMD at sites where influent chemistry precludes the use of other passive systems.     

Reduction of copper(II) by iron(II)

Laboratory and field investigations have clearly demonstrated the important role of reduced iron (Fe(II)) in reductive transformations of first-row transition metal species. However, interactions of Fe(II) and copper (Cu) are not clearly understood. This study examined the reduction of Cu(II) by Fe(II) in stirred-batch experiments at pH 5.2 and 5.5 as influenced by chloride (Cl-) concentration (0.002-0.1 M), initial metal concentration (0.1-9.1 mM), and reaction time (1-60 min) under anoxic conditions. Reduction of Cu(II) to Cu(I) by dissolved Fe(II) was rapid under all experimental conditions and the stability of the products explains the driving force for the redox reaction. Under conditions of low [Cl-] and high initial metal concentration, >40% of total Cu and Fe were removed from solution after 1 min, which accompanied formation of a brownish-red precipitate. X-ray diffraction (XRD) patterns of the precipitates revealed the presence of cuprite (Cu2O), a Cu(I) mineral, based on d-spacings located at 0.248, 0.215, 0.151, and 0.129 nm. Fourier transform infrared (FTIR) spectroscopy corroborated XRD data for the presence of Cu2O, with features located at 518, 625, and 698 cm(-1). Increasing [Cl-] stabilized the dissolved Cu(I) product against Cu2O precipitation and resulted in more Fe precipitated from solution (relative to Cu) that appears to be present as poorly crystalline lepidocrocite (gamma-FeOOH). This process may be important in anoxic soil environments, where dissolved Fe(II) levels can accumulate.     

Soil chemical changes resulting from irrigation with water co-produced with coalbed natural gas

Land application of coalbed natural gas (CBNG) co-produced water is a popular management option within northwestern Powder River Basin (PRB) of Wyoming. This study evaluated the impacts of land application of CBNG waters on soil chemical properties at five sites. Soil samples were collected from different depths (0-5, 5-15, 15-30, 30-60, 60-90, and 90-120 cm) from sites that were irrigated with CBNG water for 2 to 3 yr and control sites. Chemical properties of CBNG water used for irrigation on the study sites indicate that electrical conductivity of CBNG water (EC(w)) and sodium adsorption ratio of CBNG water (SAR(w)) values were greater than those recommended for irrigation use on the soils at the study sites. Soil chemical analyses indicated that electrical conductivity of soil saturated paste extracts (EC(e)) and sodium adsorption ratio of soil saturated paste extracts (SAR(e)) values for irrigated sites were significantly greater (P < 0.05) than control plots in the upper 30-cm soil depths. Mass balance calculations suggested that there has been significant buildup of Na in irrigated soils due to CBNG irrigation water as well as Na mobilization within the soil profiles. Results indicate that irrigation with CBNG water significantly impacts certain soil properties, particularly if amendments are not properly utilized. This study provides information for better understanding changes in soil properties due to land application of CBNG water. These changes must be considered in developing possible criteria for preserving fragile PRB ecosystems.     

Experimental oxidative dissolution of sphalerite in the Aznalcollar sludge and other pyritic matrices

After the collapse on 25 Apr. 1998 of the Aznalcóllar mine tailings dike in southwestern Spain, 45 km2 of the Guadiamar valley were covered by a pyritic sludge containing up to 2% sphalerite (ZnS). Later, the sludge was mechanically removed and calcium carbonate was plowed into the soil to immobilize heavy metals. By June 2001 more than 60% of the sulfides in the residual sludge had oxidized and soil Zn contents reached locally phytotoxic levels. Therefore, the oxidative dissolution of sphalerite in the sludge and other pyritic samples was examined. Flow-through oxidation experiments showed that: (i) about 5 and 17% of the sludge Fe and Zn were in soluble form, respectively, because the sludge sample had been partly oxidized in the field; (ii) the oxidation rates of the residual pyrite and sphalerite were similar; (iii) the overall sulfide oxidation rate was relatively unaffected by the addition of calcite; and (iv) poorly crystalline Fe (hydr)oxides containing Zn in occluded form and Zn (hydroxi)carbonates were formed in the presence of calcite. The rate of oxidation of reference sphalerite greatly increased when it was incorporated in the sludge or in a reference pyrite matrix. This enhancement was due to galvanic interaction because pyrite oxidation was depressed in the presence of sphalerite. Oxidation by Fe3+ ions was less important because the oxidation rates of native sphalerite were not greater at low than at high pH. The fast oxidation rate of sphalerite in the Aznalcóllar sludge indicates a need for quick adoption of remediation measures in similar accidents elsewhere. The use of calcite amendments has little influence on the oxidation rate but does result in the accumulation of Zn in relatively insoluble forms.     

An investigation into the likely impact of oxy-coal retrofit on fire-side corrosion behavior in utility boilers

Real-time electrochemical measurements of corrosion rate were performed to evaluate the respective corrosion rates of one boiler waterwall material (SA210) and three boiler superheater materials (T22, P91 and 347H) while firing Utah Western bituminous, Illinois high-sulfur bituminous and Powder River Basin (PRB) sub-bituminous coals in a 1.5 MW pulverized coal-fired furnace. The raw average measured corrosion rates were very low, between 0.0003 and 0.016 mm/year (0.012 and 0.63 mils/year) for most materials under air- and oxy-fired conditions. For some high-sulfur conditions measured corrosion rates were as high as 0.72 mm/year (28 mils/year). Waterwall corrosion rates decreased consistently when converting from air- to oxy-firing while superheater corrosion rates generally increased, although they were less than twice the air-fired rate under most conditions. Corrosion rates for the lower alloyed materials (SA210 and T22) increased significantly during transients from reducing to oxidizing conditions. Measured increases in the corrosion rate of 347H material under high sulfur and low temperature conditions, and associated decrease in corrosion rate at higher temperatures on this alloy, were consistent with the formation of trisulphates in the superheater deposits. The increase of corrosion rate with increased metal temperatures was demonstrated, as was the consistently repeatable nature of the observed results.     

Remediating munitions-contaminated soil with zerovalent iron and cationic surfactants

Soils contaminated from military operations often contain mixtures of HMX (octahydro-1,3,5,7-tetranitro-1,3,5,7-tetrazocine), RDX (hexahydro-1,3,5-trinitro-1,3,5-triazine), and TNT (2,4,6-trinitrotoluene) rather than a single explosive. Differences among explosives in solubility and reactivity make developing a single remediation treatment difficult. When Fe(0) was used to treat a munitions-contaminated soil, we observed high rates of destruction for RDX and TNT (98%) but not HMX. Our objective was to determine if HMX destruction by Fe(0) could be enhanced by increasing HMX solubility by physical (temperature) or chemical (surfactants) means. To determine electron acceptor preference, we treated RDX and HMX with Fe(0) in homogeneous solutions and binary mixtures. Increasing aqueous temperature (20 to 55 degrees C) increased HMX solubility (2 to 22 mg L(-1)) but did not increase destruction by Fe(0) in a contaminated soil slurry that also contained RDX and TNT. Batch experiments using equal molar concentrations of RDX and HMX demonstrated that RDX was preferentially reduced over HMX by Fe(0). By testing various surfactants, we found that the cationic surfactants (HDTMA [hexadecyltrimethylammonium bromide], didecyl, and didodecyl) were most effective in increasing HMX concentration in solution. Didecyl and HDTMA were also found to be highly effective in facilitating the transformation of HMX by Fe(0). Using HDTMA or didecyl solutions (3%, w/v) containing solid-phase HMX, we observed that 100% of the added HMX was transformed by Fe(0) in the didecyl matrix and 60% in the HDTMA matrix. These results indicate that cationic surfactants can increase HMX solubility and facilitate Fe(0)-mediated transformation kinetics but HMX destruction rates will be slowed when RDX is present.     

Hydrochemical evaluation of the Voltaian system--the Afram Plains area, Ghana

Inverse geochemical modeling from PHREEQC, and multivariate statistical methods were jointly used to define the genetic origin of chemical parameters of groundwater from the Voltaian aquifers in the Afram Plains area. The study finds, from hierarchical cluster analysis that there are two main hydrochemical facies namely the calcium-sodium-chloride-bicarbonate waters and the magnesium-potassium-sulfate-nitrate waters in the northern and southern sections, respectively, of the Afram Plains area. This facies differentiation is confirmed by the distribution of the SO(4)(2-)/Cl(-) ratio, which associates groundwater from the northern and southern sections to areas influenced by contact with evaporites and seawater, respectively. Principal component analysis (PCA) with varimax rotation using the Kaiser criterion identifies four principal sources of variation in the hydrochemistry. Mineral saturation indices calculated from both major ions and trace elements, indicate saturation-supersaturation with respect to calcite, aragonite, k-mica, chlorite, rhodochrosite, kaolinite, sepiolite, and talc, and undersaturation with respect to albite, anorthite, and gypsum in the area. Inverse geochemical modeling along groundwater flowpaths indicates the dissolution of albite, anorthite and gypsum and the precipitation of kaolinite, k-mica, talc, and quartz. Both the PCA and inverse geochemical modeling identify the incongruent weathering of feldspars as the principal factors controlling the hydrochemistry in the Afram Plains area. General phase transfer equations have been developed to characterize the geochemical evolution of groundwater in the area. A very good relationship has been established between calcite and aragonite saturation indices in the Afram Plains area, with R(2)=1.00.     

An Evaluation of Several In-Lake Restoration Techniques to Improve the Water Quality Problem (Eutrophication) of Saint-Augustin Lake,Quebec, Canada

Increasing phosphorus (P) content and decreasing water quality of Saint-Augustin Lake, Quebec City, Canada, has led to implementation of an Integrated Watershed Management Plan to restore the lake. As a part of the plan, the effects of different restoration techniques on lake water quality and biological community (i.e., biological compatibility) were assessed during an isolated water enclosure study and laboratory microcosm assay, respectively. The restoration techniques include: (i) coagulation of P by alum only (20 mg L⁻¹), (ii) active capping of sediments using a calcite layer of 10 cm, and (iii) a complete method involving both alum coagulation and calcite capping. The results showed that the total P (TP) was greatly decreased (76–95 %) by alum + calcite, followed by calcite only (59–84 %). Secchi depth was 106 % greater and chlorophyll a concentrations were declined by 19–78 % in the enclosure which received both alum and calcite. Results of the biological compatibility test showed that total phytoplankton biomass declined by 31 % in microcosms composed of alum + calcite. No significant (P > 0.05) toxic effect was found on the survival of Daphnia magna and Hyalella azteca in both alum only and alum + calcite microcosms. Although the alum + calcite technique impaired the survival of Chironomus riparius, the midge emergence was much higher compared to alum only and control. Overall, the alum + calcite application was effective in controlling P release from sediment and lowering water column P concentrations, and thus improving the water quality and aquatic life of Saint-Augustin Lake. However, the TP concentrations are still higher than the critical limit (20 μg L⁻¹) for aquatic life and the water column remained in the eutrophic state even after treatment. Increased TP concentrations, to higher than ambient levels of the lake, in the water column of all four enclosures, due to bioturbation artefact triggered by the platform installation, likely cause insufficient dosages of alum and/or calcite applied and reduced their effectiveness.     

Characterization of phosphorus species in biosolids and manures using XANES spectroscopy

Identification of the chemical P species in biosolids or manures will improve our understanding of the long-term potential for P loss when these materials are land applied. The objectives of this study were to determine the P species in dairy manures, poultry litters, and biosolids using X-ray absorption near-edge structure (XANES) spectroscopy and to determine if chemical fractionation techniques can provide useful information when interpreted based on the results of more definitive P speciation studies. Our XANES fitting results indicated that the predominant forms of P in organic P sources included hydroxylapatite, PO(4) sorbed to Al hydroxides, and phytic acid in lime-stabilized biosolids and manures; hydroxylapatite, PO(4) sorbed on ferrihydrite, and phytic acid in lime- and Fe-treated biosolids; and PO(4) sorbed on ferrihydrite, hydroxylapatite, beta-tricalcium phosphate (beta-TCP), and often PO(4) sorbed to Al hydroxides in Fe-treated and digested biosolids. Strong relationships existed between the proportions of XANES PO(4) sorbed to Al hydroxides and NH(4)Cl- + NH(4)F-extractable P, XANES PO(4) sorbed to ferrihydrite + phytic acid and NaOH-extractable P, and XANES hydroxylapatite + beta-TCP and dithionite-citrate-bicarbonate (DCB)- + H(2)SO(4)-extractable P (r(2) = 0.67 [P = 0.01], 0.78 [P = 0.01], and 0.89 [P = 0.001], respectively). Our XANES fitting results can be used to make predictions about long-term solubility of P when biosolids and manures are land applied. Fractionation techniques indicate that there are differences in the forms of P in these materials but should be interpreted based on P speciation data obtained using more advanced analytical tools.     

Atrazine, isoproturon, mecoprop, 2,4-D, and bentazone adsorption onto iron oxides

Iron oxides are important components influencing the adsorption of various inorganic and organic compounds in soils and sediments. In this study the adsorption on iron oxides of nonionic and ionic pesticides was determined as a function of solution pH, ionic strength, and pesticide concentration. The investigated iron oxides included two-line ferrihydrite, goethite, and lepidocrocite. Selected pesticides comprised atrazine (6-chloro-N2-ethyl-N4-isopropyl-1,3,5-triazine-2,4-diamine), isoproturon [3-(4-isopropylphenyl)-1,1-dimethylurea)], mecoprop [(RS)-2-(4-chloro-2-methylphenoxy)propionic acid], 2,4-D (2,4-dichlorophenoxyacetic acid), and bentazone [3-isopropyl-1H-2,1,3-benzothiadiazin-4(3H)-one 2,2-dioxide]. The adsorption of the nonionic pesticides (atrazine and isoproturon) was insignificant, whereas the adsorption of the acidic pesticides (mecoprop, 2,4-D, and bentazone) was significant on all investigated iron oxides. The adsorption capacity increased with decreasing pH, with maximum adsorption reached close to the pKa values. The addition of CaCl2 in concentrations from 0.0025 to 0.01 M caused the adsorption capacity to diminish. The adsorption of bentazone was significantly lower than the adsorption of mecoprop and 2,4-D, illustrating the importance of a carboxyl group in the pesticide structure. The adsorption capacity on the iron oxides increased in the order: lepidocrocite < goethite < two-line ferrihydrite. The maximum adsorption capacities of meco-prop and 2,4-D on goethite were found to be equivalent to the site density of singly coordinated hydroxyl groups on the faces of the dominant (110) form, suggesting that singly coordinated hydroxyl groups are responsible for adsorption. Differences in adsorption capacities between iron oxides can be explained by differences in the surface site density of singly coordinated hydroxyl groups. The maximum measured adsorption capacity of mecoprop on two-line ferrihydrite was equivalent to 0.2 mol/mol Fe.     

Removal of Cr(VI) from Cr-contaminated groundwater through electrochemical addition of Fe(II)

The conventional chemical reduction-precipitation technique in the removal of Cr(VI) from contaminated groundwater involves a two-step process whereby Cr(VI) is first reduced to Cr(III) at an acidic pH by a reducing agent and in a subsequent step, Cr(III) is precipitated as insoluble hydroxide at an alkaline pH. In a variation of this method, Fe(II) is added electrochemically to the Cr(VI) containing water. From a pure iron electrode, Fe(2+) ions are released into the solution and bring forth the reduction of Cr(VI). At the cathode, H(2)O is reduced whereby the OH(-) ions entering the solution keep the pH of the solution in the alkaline range. This latter fact greatly facilitates simultaneous reduction of Cr(VI) to Cr(III) and co-precipitation of hydroxides of trivalent Cr and Fe. On the basis of a set of experimental data, it is shown that this process is both thermodynamically and kinetically efficient, meaning, with the electrochemical method, rapid and nearly complete removal of Cr(VI) from a groundwater source with both high and low levels of Cr-contamination can be achieved. These factors make the electrochemical process superior to the conventional chemical process in remediation of Cr-contaminated groundwater.     

Nitrate reduction in the presence of wüstite

Recent strategies to reduce elevated nitrate concentrations employ metallic Fe0 as a reductant. Secondary products of Fe0 corrosion include magnetite (Fe3O4), green rust [Fe6(OH)12SO4], and wüstite [FeO(s)]. To our knowledge, no studies have been reported on the reactivity of NO3- with FeO(s). This project was initiated to evaluate the reactivity of FeO(s) with NO3- under abiotic conditions. Stirred batch reactions were performed in an anaerobic chamber over a range of pH values (5.45, 6.45, and 7.45), initial FeO(s) concentrations (1, 5, and 10 g L(-1)), initial NO3- concentrations (1, 10, and 15 mM), and temperatures (3, 21, 31, and 41 degrees C) for kinetic and thermodynamic determinations. Suspensions were periodically removed and filtered to measure dissolved nitrogen and iron species. Solid phases were characterized using X-ray diffraction (XRD) and scanning electron microscopy (SEM). Nitrate reduction by FeO was rapid and characterized by nearly stoichiometric conversion of NO3- to NH4+. Transient NO2- formation also occurred. The XRD and SEM results indicated the formation of Fe3O4 as a reaction product of the heterogeneous redox reaction. Kinetics of NO3- reduction suggested a rate equation of the type: -d[NO3-]/dt = k[FeO]0.57[H]0.22[NO3-]1.12 where k = 3.46 x 10(-3) +/- 0.38 x 10(-3) M(-1) s(-1), at 25 degrees C. Arrhenius and Eyring plots indicate that the reaction is surface chemical-controlled and proceeds by an associative mechanism involving a step where both NO3- and FeO(s) bind together in an intermediate complex.     

MODELING ACID MINE DRAINAGE ON A WATERSHED SCALE FOR TMDL CALCULATIONS1

ABSTRACT: The Cheat River of West Virginia is impaired by acid mine drainage (AMD). Fifty‐five of its river segments were placed on the 303(d) list, which required calculations of total maximum daily load (TMDL) to meet the water quality criteria for pH, total iron, aluminum, manganese, and zinc. An existing watershed model was enhanced to simulate AMD as nonpoint source load. The model divided a watershed into a network of catchments and river segments. Each catchment was divided into soil layers, which could contain pyrite, calcite and other minerals. A kinetic expression was used to simulate pyrite oxidation as a function of oxygen in the soil voids. Oxygen in the soil voids was consumed by pyrite oxidation and replenished by earth breathing. The by‐products of pyrite oxidation were calculated according to its mass action equations. Chemical equilibrium was used to account for the speciation of ferrous and ferric irons and precipitation of metal hydroxides. Simulated hydrology and water quality were compared to available data. The USEPA used the calibrated model to calculate the TMDLs in the Cheat River Watershed.     

Treatment of wastewater phosphate by reductive dissolution of iron: use of ferric oxyhydroxide media

In smaller wastewater treatment systems such as septic systems, there is an interest in the development of passive phosphorus (P) removal methods. This study tested fixed-bed filters containing ferric oxyhydroxide media for wastewater P removal in a laboratory column test and in a full-scale domestic septic system. In the column test, during 30 mo of dosing with domestic wastewater, reductive iron dissolution reactions delivered consistent moderate concentrations of Fe into solution (2.9 ± 1.6 mg L), and influent PO-P of 3.7 ± 1.0 mg L was attenuated to 0.09 + 0.04 mg L in the column effluent (98% removal). Phosphorus breakthrough at successive locations along the column indicated that in addition to sorption, mineral precipitation reactions probably also played an important role in the observed P attenuation. This was supported by electron microprobe analyses, which showed the presence of thick (20 μm) secondary Fe-rich coatings containing P on the primary ferric media grains. Assays of NaHCO-leachable and acid-extractable P on the column solids showed accumulation of up to 5.4 mg g acid-extractable P near the column inlet, but <5% of this amount was easily desorbable, further indicating P attenuation from processes other than sorption. Over 19 mo of operation, the domestic septic system also showed generally consistent increased Fe in the filter effluent (2.6 ± 1.7 mg L) and achieved 99% P removal to 0.03 ± 0.02 mg L when the effluent was subsequently oxidized in a sand filter. Ferric iron filters could be attractive options for P removal in smaller wastewater systems because of their passive nature.     

Solid phosphorus phase in aluminum- and iron-treated biosolids

Stabilization of phosphorus (P) in sewage sludge (biosolids) to reduce water-soluble P concentrations is essential for minimizing P loss from amended soils and maximizing the capacity of the soil to safely serve as an outlet for this waste material. The chemical form at which P is retained in biosolids stabilized by Al(2)(SO(4))(3) x 18H(2)O (alum) or FeSO(4) x 7H(2)O (FeSul) was investigated by scanning electron microscopy (SEM) equipped with energy-dispersive X-ray elemental spectrometry (EDXS) and by X-ray diffraction (XRD). Both treatments resulted in the formation of a Ca-P phase, probably brushite. Phosphorus was further retained in the alum-treated biosolids by precipitation of an Al-P phase with an Al/P molar ratio of about 1:1, while in the FeSul-treated biosolids, P was retained by both precipitation with Fe/P molar ratios of 1:1 or 1.5:1, and by adsorption onto newly formed Fe hydroxides exhibiting an Fe/P molar ratio of up to 11:1. All of these mechanisms efficiently reduced P solubility and are crucial in biosolids environmentally safe agronomic beneficial use for this waste product; however, each P phase formed may react differently in the amended soil, depending on soil properties. Thus, the proper P stabilization method would depend on the target soil.