Jerry M. Bigham

Schwertmannite and the chemical modeling of iron in acid sulfate waters

Abstract Analyses of ochreous sediments and associated solutions from twenty-eight mine drainage sites showed that precipitates formed at pH 6.5 or higher were composed of ferrihydrite (nominally Fe5HO8 · 4H2O) or a mixture of ferrihydrite and goethite (α-FeOOH), whereas those precipitated from waters having pH values in the range of 2.8 to 4.5 were predominantly schwertmannite (ideally Fe8O8(OH)6SO4) with trace to minor amounts of goethite. Solutions of intermediate pH values produced mixtures of ferrihydrite and schwertmannite. Only one sample, formed at pH 2.6, contained a significant amount of jarosite (H, K, Na)Fe3(OH)6(SO4)2. A solubility window of log IAPSh = 18.0 ± 2.5 was calculated for schwertmannite from selected mine drainage solutions with pH values in the range of 2.8 to 3.2. The relationship between pH and log αFe3 over the full range of drainage waters was consistent with published results from other sources, and the combined mineralogy-chemistry data were used to compute a new pe-pH diagram for the system FeSKOH that included a field of metastability for schwertmannite. The metastable nature of schwertmannite was confirmed in a long-term (1739 d) aqueous equilibrium study wherein a pure, synthetic specimen was completely transformed to goethite over a period of 543 days. The pH and computed activity of Fe 3+ in the final equilibrium solutions yielded a log KGT = 1.40 ± 0.01 for goethite. Additional field data supporting a paragenetic relationship between jarosite, schwertmannite, ferrihydrite, and goethite were obtained from a naturally acid alpine stream. Similar results were predicted from the water chemistry using a nonequilibrium reaction path model that included appropriate solubility data for the mineral phases of interest.

Removal of trace metals by coprecipitation with Fe, Al and Mn from natural waters contaminated with acid mine drainage in the Ducktown Mining District, Tennessee

Abstract This study examined the sorption of trace metals to precipitates formed by neutralization of 3 natural waters contaminated with acid mine drainage (AMD) in the former Ducktown Mining District, Tennessee. The 3 water samples were strongly acidic (pH 2.2 to 3.4) but had distinctively different chemical signatures based on the mole fractions of dissolved Fe, Al and Mn. One sample was Fe-rich (Fe=87.5%, Al=11.3%, and Mn=1.3%), another was Al-rich (Al=79.4%, Mn=18.0%, and Fe=2.5%), and the other was Mn-rich (Mn=51.4%, Al=25.7%, and Fe=22.9%). In addition, these waters had high concentrations of trace metals including Zn (37,700 to 17,400 μg/l), Cu (13,000 to 270 μg/l), Co (1,500 to 520 μg/l), Ni (360 to 75 μg/l), Pb (30 to 8 μg/l), and Cd (30 to 6 μg/l). Neutralization of the AMD-contaminated waters in the laboratory caused the formation of either schwertmannite at pH 4. Both phases were identified by XRD analyses of precipitates from the most Fe-rich water. At higher pH values (∼5) Al-rich precipitates were formed. Manganese compounds were precipitated at pH∼8. The removal of trace metals depended on the precipitation of these compounds, which acted as sorbents. Accordingly, the pH for 50% sorption (pH50) ranged from 5.6 to 7.5 for Zn, 4.6 to 6.1 for Cu, 5.4 to 7.7 for Ni, 5.9 to 7.9 for Co, 3.1 to 4.3 for Pb, and 5.5 to 7.7 for Cd. The pH dependence of sorption arose not only because of changes in the sorption coefficients of the trace metals but also because the formation and composition of the sorbent was controlled by the pH, the chemical composition of the water, and the solubilities of the oxyhydroxide-sulfate complexes of Fe, Al, and Mn.

Influence of pH on mineral speciation in a bioreactor simulating acid mine drainage

Abstract Mineral precipitates formed under conditions representative of acid mine drainage were prepared by oxidizing 0.1 M FeS04 · 7H20 solutions at 24°C and pH 2.3, 2.6, 3.0, 3.3 and 3.6 using a bioreactor and a strain ofThiobacillus ferrooxidans. The oxidation of dissolved Fe2+ was monitored colorimetrically and was completed within 90 to 120 h at all pHs. Schwertmannite, Fe8O8(OH)6SO4, was a major component of the precipitates and was the only phase formed at pH 3.0. Jarosite, (H,Na,K)Fe3(OH)6(SO4)2, increased in abundance with decreasing pH whereas goethite, α-FeOOH, appeared at pH 3.3 and 3.6. A similar relationship between pH and mineralogy has been reported in natural specimens of mine drainage ochres.

Charge reduction, octahedral charge, and lithium retention in heated, Li-saturated smectites

Reference smectites were examined to determine relationships between Li uptake, cation-exchange capacity (CEC), and octahedral layer charge after Li saturation and heating at 250°C (Hofmann-Klemen effect). Direct measurements of exchangeable Li after heating led to overestimates of charge reduction due to entrapment of Li in collapsed interlayers. Expansion of interlayers by sequential washings with 1 N MgCl2, 0.01 N MgCl2, and ethanol and subsequent determinations of exchangeable Mg provided accurate measurements of reduced charge. The CEC reductions observed in dioctahedral samples as a result of Li saturation and heating equaled octahedral charge values derived from published mineral formulae, and interlayer charge estimates obtained by alkylammonium exchange confirmed that measured CEC reductions were a consequence of uniform decreases in octahedral layer charge.Dioctahedral specimens retained 1 to 10 meq/100 g of non-exchangeable Li in excess of CEC reduction and were acidified in direct proportion to their total Fe contents, apparently as a result of the deprotonation of structural hydroxyl groups. Mild acid treatment reprotonated these hydroxyl groups, released excess Li, and resulted in total Li contents comparable to measured CEC reductions. Heating (250°C) Mg-saturated hectorite induced a loss of octahedral Li, acidification, and a reduction of CEC, indicating that Mg had partially replaced octahedral Li. These results suggest that octahedral Li is mobile at low temperatures and that cation movement into or out of the octahedral sheet is favored if the layer charge is reduced.

Influence of sulfate on Fe-oxide formation; comparisons with a stream receiving acid mine drainage

An ochreous precipitate isolated from a stream receiving acid-sulfate mine drainage was found to consist primarily of goethite and lesser amounts of ferrihydrite-like materials. The Fe-oxide fraction, including goethite, was almost totally soluble in acid ammonium oxalate. Similar materials were produced in the laboratory by hydrolysis of ferric nitrate solutions containing 250 to 2000 μg/ml sulfate as Na2SO4. Initial precipitates of natrojarosite transformed to Fe-oxides upon aging for 30 days at pH 6.0. The proportion of goethite in the final products decreased with increasing sulfate (SO4/Fe = 0.2 to 1.8) in the initial hydrolysis solutions; only ferrihydrite-like materials were produced at SO4/Fe ratios > 1.5. Variations in SO4/Fe solution ratios also produced systematic changes in the color (10R to 7.5YR) and surface areas (49 to 310 m2/g) of the dried precipitates, even though total S contents were relatively constant at 2.5 to 4.0%.

Sorption of trace metals to an aluminum precipitate in a stream receiving acid rock-drainage; Snake River, Summit County, Colorado

The quality of water in streams that are contaminated by acid drainage from mines and from the weathering of mineralized rocks improves as the water flows downstream. The purpose of this study was to investigate the geochemical processes that occur in one such stream and to determine the fate of the trace metals that are removed from the water. The stream chosen for this purpose was the Snake River, Summit County, Colorado, which is affected by natural acid rock-drainage (ARD) containing SO4, Al, Fe, and various trace elements such as Zn, Cu, Pb, Ni, and others. Most of the Fe in the Snake River is removed from solution by the oxidation of Fe2+ to Fe3+ and the subsequent precipitation of Fe-oxyhydroxides that form a massive ferricrete deposit near the springs that feed the river. Further downstream, the Snake River (pH=3.0) mixes with water from Deer Creek (pH= 7.0) thereby increasing its pH to 6.3 and causing SO4-rich precipitates of Al-oxyhydroxide to form. The precipitates and associated organic C complexes sorb trace metals from the water and thus have high concentrations of certain elements, including Zn (540–11,400 ppm), Cu (34–221 ppm), Pb (90–340 ppm), and Ni (11–197 ppm). The concentrations of these elements in the precipitates that coat the streambed rise steeply in the zone of mixing and then decline downstream. The trace element concentrations of the water in the mixing zone at the confluence with Deer Creek decrease by 75% or more and are up to 3 orders of magnitude lower than those of the precipitates. Sorption curves for Zn, Cu, Pb, Ni, and SO4 were derived by stepwise neutralization of a sample of Snake River water (collected above the confluence with Deer Creek) and indicate that the trace metals are sorbed preferentially with increasing pH in the general order Pb, Cu, Zn, and Ni. Sulfate is removed between pH 4 and 5 to form an Al-hydroxysulfate and/or by sorption to microcrystalline gibbsite. The sorption data determined from the neutralization experiment were used to account for the downstream decrease of trace-metal concentrations in the precipitates. The results of this study demonstrate that the partitioning of trace metals in the Snake River is not only a function of pH, but also depends on the progressive removal of trace metals as the water of the Snake River flows through its confluence with Deer Creek. The chemical composition of the water also determines what compounds precipitate with increasing pH.

Assessing mine drainage pH from the color and spectral reflectance of chemical precipitates

The pH of mine impacted waters was estimated from the spectral reflectance of resident sediments composed mostly of chemical precipitates. Mine drainage sediments were collected from sites in the Anthracite Region of eastern Pennsylvania, representing acid to near neutral pH. Sediments occurring in acidic waters contained primarily schwertmannite and goethite while near neutral waters produced ferrihydrite. The minerals comprising the sediments occurring at each pH mode were spectrally separable. Spectral angle difference mapping was used to correlate sediment color with stream water pH (r 2 =0.76). Band-center and band-depth analysis of spectral absorption features were also used to discriminate ferrihydrite and goethite and/or schwertmannite by analyzing the 4 T1 6 A1 crystal field transition (900– 1000 nm). The presence of these minerals accurately predicted stream water pH (r 2 =0.87) and provided a qualitative estimate of dissolved SO4 concentrations. Spectral analysis results were used to analyze airborne digital multispectral video (DMSV) imagery for several sites in the region. The high spatial resolution of the DMSV sensor allowed for precise mapping of the mine drainage sediments. The results from this study indicate that airborne and space-borne imaging spectrometers may be used to accurately classify streams impacted by acid vs. neutral-to-alkaline mine drainage after appropriate spectral libraries are developed. Published by Elsevier Science Ltd.

QUANTIFICATION AND CHARACTERIZATION OF MAGHEMITE IN SOILS DERIVED FROM VOLCANIC ROCKS IN SOUTHERN BRAZIL

Many soils developed from volcanic rocks in southern Brazil exhibit spontaneous magnetization caused by the presence of fine-grained maghemite (γ-Fe2O3), but few attempts were made to quantify or characterize this important soil component. To that end, clays were separated from freely drained soils derived from acid (≥63% SiO2), intermediate (54–62% SiO2), and basic (≤53% SiO2) igneous rocks produced by the Paraná flood volcanism. The sample set included soils with a wide range of pedogenic development on different landscape positions. The Fe oxide mineralogy of these samples was examined by using a combination of selective dissolution, magnetic susceptibility, and X-ray diffraction (XRD) techniques. Hematite and maghemite were the primary Fe oxides in mature soils (Oxisols, Ultisols, and Alfisols) developed from basic rocks; whereas goethite was dominant in all other soils, especially those formed from acid-intermediate rocks. The association of maghemite with basic rock materials suggests that it was primarily formed by oxidation of lithogenic magnetite. A strong, positive correlation (R2 = 0.89) was obtained between mass specific magnetic susceptibility (χ) of the clay fractions and maghemite contents estimated by XRD. Either method could be used for quantitative analyses, but χ was more sensitive than XRD at low maghemite concentrations (<2 wt. %). The clay-sized maghem-ites were superparamagnetic with an estimated value for the mass specific magnetic susceptibility (χlf) value of 91,000 × 10−8 m3 kg−1 and frequency dependent variations of 10–15%. The maghemites also had low unit cell constants, which, if attributed entirely to replacement of Fe by Al, would correlate with Al substitutions in the range of 5–16 mole %. Selective dissolution of the soil maghemites was achieved by treatment of Fe oxide concentrates with 1.8 M H2SO4 at 75°C for 2 h.

Formation of Fe-sulfides in cultures of sulfate-reducing bacteria.

The purpose of this study was to synthesize Fe-sulfides produced with sulfate-reducing bacteria under experimental laboratory conditions. Fe-sulfides were precipitated with biologically produced sulfide in cultures growing at 22, 45, and 60 degrees C for up to 16 weeks. Abiotic controls were prepared by reacting liquid media with Na(2)S solutions. Precipitates were collected anaerobically, freeze-dried and analyzed by X-ray diffraction. Additional analyses included total Fe and S content, magnetic susceptibility, specific surface area, and scanning electron microscopy. Mackinawite (FeS) and greigite (Fe(3)S(4)) were the dominant iron sulfide phases formed in sulfate-reducing bacterial cultures. An increase in the incubation temperature from 22 to 60 degrees C enhanced the crystallinity of the Fe-sulfides. Generally, greigite was more prevalent in abiotic samples and mackinawite in biogenic materials. Pyrite (FeS(2)) was also found in abiotic precipitates. Abiotic samples had a higher magnetic susceptibility because of the greigite and displayed improved crystallinity compared to biotic materials.

Properties of iron oxides in streams draining the Loess Uplands of Mississippi

Abstract Iron oxide precipitates are abundant in small stream systems of NW Mississippi, USA especially during the wet winter months. The properties of these specific materials are unknown even though they have the potential to influence soil physical properties and adsorb chemical pollutants in sediment environments. Streamwater and associated precipitates were collected from 4 representative streams at Cedar Creek (CC), Lees Creek (LC), Spring Creek (SC), and Toby Creek (TC) during winter flow periods. Precipitate specimens were characterized for mineralogy, color, and solubility in oxalate (o), dithionite (d), and HNO 3 . Chemical composition of the water was dominated by Ca, Na, Mg, and K, in that order, at an average pH of 7.0. X-ray diffraction (XRD) and differential scanning calorimeter (DSC) data indicated that the precipitates were primarily poorly ordered ferrihydrite (CC, TC) and lepidocrocite (LC, SC). The Fe o /Fe d ratios were 0.40 (CC), 0.68 (LC), 0.66 (SC), and 0.67 (TC). Organic C contents were 80.6, 38.0, 63.0, and 51.3 g kg −1 for the same samples. Precipitate color was uniform among sites, averaging 6.7 YR 4.8/6.2. After oxalate extraction, redness increased slightly in the CC and SC specimens, and decreased in the others. Extraction with dithionite depleted the red color in all specimens, but had less effect on the CC and SC samples which retained hues at 7.9 and 7.3 YR, respectively. Dithionite extractable P equaled 1.02 (CC), 0.72 (LC), 0.56 (SC), and 0.99 (TC) g kg −1 . The results from this study indicated that: (1) the precipitates are either primarily poorly ordered ferrihydrite or lepidocrocite; (2) the solubility of ferrihydrite in both oxalate and dithionite is influenced by C contents; and (3) the redder, ferrihydrite specimens contain the greatest P concentrations.