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Ferric iron (Fe(III)) oxyhydroxides commonly precipitate at neutral pH and in highly oxygenated conditions in waterways receiving acid mine drainage, degrading stream benthic communities by smothering of habitat, primary producers, and aquatic invertebrates. Stream mesocosms were used to expose naturally colonized benthic communities to a gradient of ferric Fe (0-15 mg/L) for 14 days to estimate the effects of Fe precipitates on primary production, larval and emerging adult aquatic insects, and the macroinvertebrate community structure. Community composition was significantly altered at concentrations near or below the US Environmental Protection Agency chronic Fe criterion (1.0 mg/L). Iron exposure significantly decreased larval and emerging adult abundances of Baetidae (mayfly) and Chironomidae (Diptera); however, while Simuliidae (Diptera) larvae were not reduced by the Fe treatments, abundance of emerged adults significantly decreased. Iron substantially decreased the colonization biomass of green algae and diatoms, with estimated EC

The air-cathode fuel cell (AC-FC) technology provides a facile approach to in situ utilize Fe2+ in acid mine drainage (AMD) for the fabrication of iron oxide/carbon composite with electro-Fenton (EF) catalytic activity. Herein, the impacts of coexisting metal cations other than the Fe2+ in AMD on such an EF catalyst fabrication process are investigated. The results show that coexisting metal cations are able to be introduced into the Fe3O4/GF composite and influence iron content in it. The Ni2+, Zn2+, Al3+, and Cu2+ in AMD lower iron content in the prepared composite and thus present a detrimental effect on its EF catalytic activity. In comparison, the Co2+ and Mn2+ hardly affect iron content in the composite. Instead, they are doped into the Fe3O4 structure to give mixed-metal oxides with enhanced EF catalytic activities. Practice on the treatment of real AMDs suggests the practical effectiveness of AC-FC technology for the simultaneous removal of heavy metal cations and fabrication of heterogeneous EF c...

Three different iron oxide-based sorption media samples were tested for removal of phosphorus (P) from fish hatchery effluents using fixed bed processing. Two of the media samples were derived from residuals produced by the treatment of acid mine drainage, which were then compared to granular ferric hydroxide (GFH), a commercially available sorption medium. All of the media types removed from 50 to 70% of the P from the incoming aquaculture wastewater over 70–175 days of operation without regeneration. In some of the sorption trials, the GFH media showed superior adsorption in the earlier stages of the trial, but the GFH appeared to reach saturation more quickly, so that media performance was similar – at about 60% removal of P – over a longer time period of 175 days. Media regeneration tests were also conducted for both the commercial and mine drainage media, and demonstrated longer term performance, with overall P removal of 50–55%, over 223 days of total operation, with the advantages of phosphorus recycle and media reuse.

Pyrrhotite is an iron deficient, low nickel content sulfide mineral that is commonly associated with pentlandite, a nickel-rich sulfide; and are both main components of the nickel ore mined in Sudbury. Pyrrhotite tailings generated in the concentration of Ni ores are stored in tailing reservoirs and presents serious environmental risks including acid mine drainage. This study investigated the potential of converting pyrrhotite into a valuable resource through the use of fluidized bed roasting, in which the mineral will be oxidized to produce iron oxide and SO2 gas. These products can then be used to create iron for high-grade steel and elemental sulfur. Thermogravimetric analysis of Sudbury pyrrhotite was performed to study the oxidation kinetics, supporting the feasibility of this process. Further, energy and materials balance was carried out to establish the basic parameters of a possible roasting process.

Acid mine drainage (AMD) contains a large amount of ferrous iron and the recovery of iron oxides from the AMD has been of extensive research interest. Here we report a novel air-cathode fuel cell strategy to in-situ utilize ferrous iron in the AMD for the fabrication of heterogeneous electro-Fenton catalysts. Three types of nano-structured iron oxide/graphite felt (GF) composites, including FeOOH/GF, Fe 2 O 3 /GF and Fe 3 O 4 /GF, were fabricated from a synthetic AMD and their catalytic activities towards the electro-Fenton reaction were evaluated at neutral pH with Rhodamine B (RhB) as a probe pollutant. The electro-Fenton system with GF cathode only removed 30 ± 1.4% of RhB after 120 min of reaction. In comparison, RhB removal efficiencies were significantly improved to 62.5 ± 2.0%, 95.4 ± 0.9% and 95.6 ± 0.7% when the FeOOH/GF, Fe 2 O 3 /GF and Fe 3 O 4 /GF composites were used as the cathodes, respectively. Among the three types of composites, the Fe 3 O 4 /GF exhibited the highest electro-Fenton catalytic activity whereas the lowest activity was observed for the FeOOH/GF. The decomposition of H 2 O 2 on the iron oxides followed a completely surface-catalyzed mechanism in which the iron oxides maintained their structures without leaching of iron species. The air-cathode fuel cell technology has a potential for iron recovery from the AMD, and provides an effective way for fabricating heterogeneous electro-Fenton catalyst with high catalytic activity and good stability.

To investigate the potential use of iron oxides originating from acid mine drainage (AMD), iron oxide coated sand (IOCS) was prepared from AMD and used to test arsenic adsorption. Batch tests were conducted to study the adsorption kinetics and isotherms of arsenic using IOCS. The maximum adsorption capacities of the IOCS for As(III) and As(V) were 56.6 μg g−1 and 99.0 μg g−1, respectively, at pH 7. Based on these results, IOCS fabricated from AMD had high arsenic adsorption capacities and can reuse the iron oxide in AMD to effectively remove arsenic in water purification systems.

Acid mine drainage (AMD) constitutes a serious environmental problem in mining areas due to the acidification of soils and aquatic systems, and the release of toxic metals. Many of the pollutants that occur in AMD display a high affinity for the surfaces of the aluminium and iron oxides that are typically present in systems affected by AMD. This binding affinity reduces the mobility of trace metals and metalloids, such as copper and arsenic, thus helping to mitigate contamination of aquatic systems. In the present study, water samples and iron-rich bed sediments were collected in areas affected by copper mining activities. A loose ochre-coloured precipitate occurring on the banks of a river close to an abandoned tungsten and tin mine was also sampled. The composition of the precipitate was established, and adsorption experiments were performed with copper and arsenate ions to determine the ability of natural iron precipitates to reduce the concentration of these ions in solution. Surface complexation models provided a good description of the behaviour of natural iron oxides in terms of copper and arsenate retention. Use of this type of model enables prediction of the distribution of pollutants between the solid and solution phases and analysis of their mobility in relation to environmental conditions (pH, ionic strength, presence of competing species, etc.).

Acid mine drainage (AMD) is a major environmental problem affecting tens of thousands of kilometers of waterways worldwide. Passive bioremediation of AMD relies on microbial communities to oxidize and remove iron from the system; however, iron oxidation rates in AMD environments are highly variable among sites. At Scalp Level Run (Cambria County, PA), first-order iron oxidation rates are 10 times greater than at other coal-associated iron mounds in the Appalachians. We examined the bacterial community at Scalp Level Run to determine whether a unique community is responsible for the rapid iron oxidation rate. Despite strong geochemical gradients, including a >10-fold change in the concentration of ferrous iron from 57.3 mg/liter at the emergence to 2.5 mg/liter at the base of the coal tailings pile, the bacterial community composition was nearly constant with distance from the spring outflow. Scalp Level Run contains many of the same taxa present in other AMD sites, but the community is dominated by two strains of Ferrovum myxofaciens , a species that is associated with high rates of Fe(II) oxidation in laboratory studies. IMPORTANCE Acid mine drainage pollutes more than 19,300 km of rivers and streams and 72,000 ha of lakes worldwide. Remediation is frequently ineffective and costly, upwards of $100 billion globally and nearly $5 billion in Pennsylvania alone. Microbial Fe(II) oxidation is more efficient than abiotic Fe(II) oxidation at low pH (P. C. Singer and W. Stumm, Science 167:1121–1123, 1970, https://doi.org/10.1126/science.167.3921.1121 ). Therefore, AMD bioremediation could harness microbial Fe(II) oxidation to fuel more-cost-effective treatments. Advances will require a deeper understanding of the ecology of Fe(II)-oxidizing microbial communities and the factors that control their distribution and rates of Fe(II) oxidation. We investigated bacterial communities that inhabit an AMD site with rapid Fe(II) oxidation and found that they were dominated by two operational taxonomic units (OTUs) of Ferrovum myxofaciens , a taxon associated with high laboratory rates of iron oxidation. This research represents a step forward in identifying taxa that can be used to enhance cost-effective AMD bioremediation.

The formation, transformation and surface chemistry of iron oxides is geologically important in surface waters polluted by acid mine drainage (AMD). The geochemical behaviour of these oxides controls the availability and mobility of contaminants in such highly polluted systems. The low pH values, together with the presence of large amounts of sulphate, favour the formation of schwertmannite, which is a metastable iron oxide that is transformed to goethite under oxic conditions. However, in copper mining environments, co-precipitation of iron and copper ions is expected and therefore the surface chemistry of the iron oxides present in these systems may be different. Several schwertmannite samples were prepared in the presence of high concentrations of sulphate and different concentrations of copper to simulate copper-rich mining environments. Long-term transformation experiments were conducted to study the mineral oxide stability and variations in surface chemistry produced over a period of 15 months. Schwertmannite-like particles were initially formed, but sulphate release and the dissolution and re-precipitation of iron and copper ions occurred under more acidic conditions throughout the experiment, which led to the formation of goethite-like particles. The capacity for arsenate adsorption was highest in the initial schwertmannite-like particles, and arsenate mobility increased in the presence of more stable iron mineral phases that were formed throughout the transformation experiment.

Iron oxide particles recovered from acid mine drainage represent a potential low-cost feedstock to replace reagent-grade chemicals in the production of goethite, ferrihydrite or magnetite with relatively high purity. Also, the properties of iron oxides recovered from acid mine drainage mean that they can be exploited as catalysts and/or adsorbents to remove azo dyes from aqueous solutions. The main aim of this study was to recover iron oxides with relatively high purity from acid mine drainage to act as a catalyst in the oxidation of dye through a Fenton-like mechanism or as an adsorbent to remove dyes from an aqueous solution. Iron oxides (goethite) were recovered from acid mine drainage through a sequential precipitation method. Thermal treatment at temperatures higher than 300 °C produces hematite through a decrease in the BET area and an increase in the point of zero charge. In the absence of hydrogen peroxide, the solids adsorbed the textile dye Procion Red H-E7B according to the Langmuir model, and the maximum amount adsorbed decreased as the temperature of the thermal treatment increased. The decomposition kinetics of hydrogen peroxide is dependent on the H(2)O(2) concentration and iron oxides dosage, but the second-order rate constant normalized to the BET surface area is similar to that for different iron oxides tested in this and others studies. These results indicate that acid mine drainage could be used as a source material for the production of iron oxide catalysts/adsorbents, with comparable quality to those produced using analytical-grade reagents.

Lignite (PK), bituminous (FI) and biomass (SE) fly ashes (FAs) were mineralogically and geochemically characterised, and their element leachability was studied with batch leaching tests. The potential for acid neutralisation (ANP) was quantified by their buffering capacity, reflecting their potential for neutralisation of acid mine drainage. Quartz was the common mineral in FAs detected by XRD with iron oxide, anhydrite, and magnesioferrite in PK, mullite and lime in FI, and calcite and anorthite in SE. All the FAs had high contents of major elements such as Fe, Si, Al and Ca. The Ca content in SE was six and eight times higher compared to PK and FI, respectively. Sulphur content in PK and SE was one magnitude higher than FI. Iron concentrations were higher in PK. The trace element concentrations varied between the FAs. SE had the highest ANP (corresponding to 275 kg CaCO3 tonne−1) which was 15 and 10 times higher than PK and FI, respectively. The concentrations of Ca2+, SO4 2−, Na+ and Cl− in the leachates were much higher compared to other elements from all FA samples. Iron, Cu and Hg were not detected in any of the FA leachates because of their mild to strong alkaline nature with pH ranging from 9 to 13. Potassium leached in much higher quantity from SE than from the other ashes. Arsenic, Mn and Ni leached from PK only, while Co and Pb from SE only. The concentrations of Zn were higher in the leachates from SE. The FAs used in this study have strong potential for the neutralisation of AMD due to their alkaline nature. However, on the other hand, FAs must be further investigated, with scaled-up experiments before full-scale application, because they might leach pronounced concentrations of elements of concern with decreasing pH while neutralising AMD.

Fe(II) and acidity are the most commonly encountered contaminants in acid mine drainage (AMD). Passive treatment for AMD involves addition of alkalinity, aerobic processes that result in oxidation of Fe(II) to Fe(III) oxides, and anoxic treatments in which sulfate is reduced to sulfide with consequent precipitation of Fe(II) sulfides. Alkalinity is usually provided by dissolution of limestone in passive treatments or by addition of lime or caustic in active systems. This paper focuses on the chemistry of AMD treatment, the mechanisms and the rates of oxidation of Fe(II) to produce Fe(III) oxides and strategies that can be used to manipulate the treatment chemistry in order to control the rate of oxidation and the quality of the residual Fe(III) oxides.

This research investigated to reduce mass of heavy metals in AMD(acid mine drainage) by microbial mats formed on the channel bed. As, Cd, Cu, Fe, Mn and Zn components were monitored in water and microbial mats, at three points (AMD1, AMD2 and AMD3), in a total of six times. Average daily discharge mass of heavy metals was highest in July, Fe component contained more than 76% of total discharge mass. Discharge mass of heavy metals of AMD and heavy metal contents in microbial mats decreased with downstream at channel. Heavy metal components that average daily discharge mass is over 0.5 kg were Fe, Cu and Zn, and they were highest in July. Average removal efficiency of heavy metals in AMD was highest about 21% in Fe, this microbial mats were due to form from precipitation of Fe component in AMD by aerobic iron bacteria. Relative content for As component in microbial mats than AMD was over 16 times, this As components were due to absorb at iron oxide and iron hydroxide on the surface of microbial mats.

Acid mine drainage (AMD) is an important contributor to surface water pollution due to the release of acid and metals. Fe(II) in AMD reacts with dissolved oxygen to produce iron oxide precipitates, resulting in further acidification, discoloration of stream beds, and sludge deposits in receiving waters. It has recently been shown that new fuel cell technologies, based on microbial fuel cells, can be used to treat AMD and generate electricity. Here we show that this approach can also be used as a technique to generate spherical nano-particles of iron oxide that, upon drying, are transformed to goethite (α-FeOOH). This approach therefore provides a relatively straightforward way to generate a product that has commercial value. Particle diameters ranged from 120 to 700 nm, with sizes that could be controlled by varying the conditions in the fuel cell, especially current density (0.04-0.12 mA/cm(2)), pH (4-7.5), and initial Fe(II) concentration (50-1000 mg/L). The most efficient production of goethite and power occurred with pH = 6.3 and Fe(II) concentrations above 200 mg/L. These results show that fuel cell technologies can not only be used for simultaneous AMD treatment and power generation, but that they can generate useful products such as iron oxide particles having sizes appropriate for used as pigments and other applications.

Simultaneous analysis of micro-X-ray diffraction (μ-XRD) and micro-X-ray fluorescence (μ-XRF) based on synchrotron light sources, and electron microprobe (EMP) analyses, were performed on iron terrace samples taken from Tinto-Odiel river system from the Iberian Pyrite Belt (IBP, SW Iberian Peninsula). Iron terraces are formed during the oxidation and precipitation of dissolved iron along the riverbeds impacted by acid mine drainage (AMD). This paper includes the study of actively-forming current terraces and fossil terraces isolated from the stream courses due to the river migration over time. The results of the study of current terrace samples from AMD-affected streams of two IPB abandoned mines (Tinto Santa Rosa and Cueva de la Mora) showed that fresh precipitates at the surface are composed primarily of metastable schwertmannite, which is gradually transformed at depth over short-time scales into goethite. Sediments of ancient terraces are composed mainly of goethite, which most likely originated from the re-crystallization of a precursor schwertmannite. However, at century-time scale, goethite partially re-crystallizes to hematite due to diagenetic processes. The transformation rate of goethite into hematite is negatively correlated with grain size and the crystallinity of goethite. Moreover, this transformation is accompanied by an increase in grain size and a decrease in surface area of hematite, and a concomitant decrease in arsenic trapped in the solid. This increase in the arsenic mobility during the diagenetic maturation should be considered in the development of conceptual and analytical models describing long-term fate, transport and bioavailability of arsenic in environmental systems.

The Tessier sequential extraction scheme (SES) was applied to sediments from the Odiel river catchment (Iberian Pyritic Belt, SW of Spain), one of the most acid rivers on Earth, to assess the chemical association (exchangeable, carbonatic, bound to manganese and iron oxides, bound to organic matter and residual mineral) of heavy metals (Zn, Cd, Pb, Cu, Cr, Mn, Ni, Fe, and Hg). Sediments are very heterogeneous in their textural characteristics, showing different grain size. Twenty-seven samples were studied from from areas along the Odiel River, from the source to the mouth, with special interest in the Odiel Marshes Natural Park due to its ecological significance. Samples were classified as sandy (especially at the river mouth with low iron oxide and organic matter content) and clay-silty (in the middle of the river catchment with high iron oxide content). The numerous sandy samples with low pH values explain the low levels of metals upstream, although potential metals contributions arise from mining and ore. However, the presence of sulfate in the mining area and carbonate at the mouth may explain the high presence of lead and iron in these sandy zones. Some percentage of mobile Ni, Cu, and Zn were detected in the mining area, but the elevated relative percentage of exchangeable Cd in the estuary is even more remarkable. The percentage of Zn bound to carbonate is considerable in the catchment but especially in the estuary. However, Cu is only detected in the carbonate phase downstream, in spite of the low concentration of carbonate, which represents a drawback in the application of the Tessier SES to these types of samples. Finally, relatively high percentages of residual, non-mobile, Hg and Pb were observed, in the estuarine and mining areas, respectively. Sand, lime, and clay fractions of representative samples from Areas I, II, and III were used in a metal speciation study. Mainly, the elements analyzed had accumulated in the non-residual fractions. In the mining area of the Pyrite Belt, the elements analyzed are mainly bound to Fe–Mn oxides (Fe + Mn + Cu + Cr + Pb + Mn ± Zn) and the organic matter/sulfide fraction (Ni + Zn + Hg ± Cd), independent of sediment grain size. In conclusion, we show that the results of the study of chemical speciation in sediments from acid rivers are independent of the sediment grain size considered.

The synthesis of magnetite nanoparticles has been the focus of numerous recent research efforts, with emerging focus on environmental applications. In previous research, reagent-grade chemicals have been used as the iron source in magnetite nanoparticle synthesis, which presents an economic challenge to the application of this technology in areas such as water and wastewater treatment. It is known that acid mine drainage (AMD) from the Mid Appalachian coal fields is low in pH and high in dissolved metals, of which iron is most abundant. In this study, ferric iron recovered from AMD via an oxidation-selective precipitation process was used as feed stock to synthesize magnetite nanoparticles by coprecipitation of ferric and ferrous iron at the pH 9.5 under an inert atmosphere. Based on X-ray diffraction analysis, the iron oxide phase in the black precipitate was magnetite. Through scanning and transmission electron microscopic studies, it was demonstrated that most of the magnetite particles ranged from 10 to 15 nm and were spheroidical or cubic in shape. Thus, the synthesis of magnetite nanoparticles with the iron recovered from AMD was technically feasible. Consequently, the need for low-cost raw feed stocks for nanoparticle manufacturing was addressed, providing additional opportunities for future application of magnetite nanoparticles in environmental engineering.

Mining-impacted streams have been shown to undergo diel (24-h) fluctuations in concentrations of major and trace elements. Fisher Creek in south-central Montana, USA receives acid rock drainage (ARD) from natural and mining-related sources. A previous diel field study found substantial changes in dissolved metal concentrations at three sites with differing pH regimes during a 24-h period in August 2002. The current work discusses follow-up field sampling of Fisher Creek as well as field and laboratory experiments that examine in greater detail the underlying processes involved in the observed diel concentration changes. The field experiments employed in-stream chambers that were either transparent or opaque to light, filled with stream water and sediment (cobbles coated with hydrous Fe and Al oxides), and placed in the stream to maintain the same temperature. Three sets of laboratory experiments were performed: (1) equilibration of a Cu(II) and Zn(II) containing solution with Fisher Creek stream sediment at pH 6.9 and different temperatures; (2) titration of Fisher Creek water from pH 3.1 to 7 under four different isothermal conditions; and (3) analysis of the effects of temperature on the interaction of an Fe(II) containing solution with Fisher Creek stream sediment under non-oxidizing conditions. Results of these studies are consistent with a model in which Cu, Fe(II), and to a lesser extent Zn, are adsorbed or co-precipitated with hydrous Fe and Al oxides as the pH of Fisher Creek increases from 5.3 to 7.0. The extent of metal attenuation is strongly temperature-dependent, being more pronounced in warm vs. cold water. Furthermore, the sorption/co-precipitation process is shown to be irreversible; once the Cu, Zn, and Fe(II) are removed from solution in warm water, a decrease in temperature does not release the metals back to the water column.

Ochre, consequence of acid mine drainage (AMD), is iron oxides-rich soil pigments that can be found in the water drainage from historic base metal and coal mines. The anaerobic strains of Geobacter sulfurreducens and Shewanella denitrificans were used for the microbial reduction of iron from samples of ochre collected from Skelton Beck (Saltburn Orange River, NZ 66738 21588) in Northeast England. The aim of the research was to determine the ability of the two anaerobic bacteria to reduce the iron present in ochre and to determine the rate of the reduction process. The physico-chemical changes in the ochre sample after the microbial reduction process were observed by the production of zero-valent iron which was later confirmed by the detection of elemental Fe in XRD spectrum. The X-Ray fluorescence (XRF) results revealed that 69.16 and 84.82% of iron oxide can be reduced using G. sulfurreducens and S. denitrificans respectively after 8 days of incubation. These results could provide the basis for the development of a biohydrometallurgical process for the production of elemental iron from ochre sediments.

Mining activities at Falu copper mine in Sweden started around the year 1080 AD and continued until 1993. During all these centuries, the acid mine drainage has caused low pH values and high metal ...

In this paper the biological ferrous iron oxidation in flooded packed bed reactors is studied. Bacterial oxidation of ferrous iron is a potential industrial process for the treatment of acid mine drainage and in the regeneration of ferric iron as a leaching agent in hydrometallurgical processes. The aim of this work is the development of a reactor capable of attaining the oxidation rates demanded by industrial processes, which are higher than those shown in the literature. The bioreactor consists of a polymethylmetacrylate column randomly packed with siliceous stone particles with inlets for fresh medium and air at the bottom from where they flood the reactor. The performance of ferrous iron biooxidation reactors is strongly improved by applying this bioreactor design.

Pore water from a wetland receiving acid mine drainage was studied for its iron and natural organic matter (NOM) geochemistry on three different sampling dates during summer 1994. Samples were obtained using a new sampling technique that is based on screened pipes of varying length (several centimeters), into which dialysis vessels can be placed and that can be screwed together to allow for vertical pore-water sampling. The iron concentration increased with time (through the summer) and had distinct peaks in the subsurface. Iron was mainly in the ferrous form; however, close to the surface, significant amounts of ferric iron (up to 40% of 2 mmol L-1 total iron concentration) were observed. In all samples studied, iron was strongly associated with NOM. Results from laboratory experiments indicate that the NOM stabilizes the ferric iron as small iron oxide colloids (able to pass a 0.45μm dialysis membrane). We hypothesize that, in the pore water of the wetland, the high NOM concentrations (>100 mg C L-1) allow formation of such colloids at the redoxcline close to the surface and at the contact zone to the adjacent oxic aquifer. Therefore, particle transport along flow paths and resultant export of ferric iron from the wetland into ground water might be possible.

The passive treatment of abandoned mine drainage using wetlands will produce a significant amount of iron rich sludge which will require costly removal and disposal. An alternative to disposal may be the use of this iron oxide material as pigments which could defray some of these costs. In this research, iron deposits from five alkaline mine drainage wetlands were collected and a series of standard tests were run. The tests included loss on ignition, moisture, pH, acid soluble metals, oil absorption, and water soluble matter. The results of these tests were compared to those achieved using commercially available natural and synthetic iron oxides. The results indicate that iron oxides from constructed wetlands have chemical properties that are intermediate to those of natural and synthetic iron oxide products.

Acid mine drainage streams in the Rocky Mountains typically have few algal species and abundant iron oxide deposits which can sorb phosphate. An instream injection of radiolabeled phosphate (32P0,) into St. Kevin Gulch, an acid mine drainage stream, was used to test the ability of a dominant algal species, Ulothrix sp., to rapidly assimilate phosphate. Approximately 90% of the injected phosphate was removed from the water column in the 175-m stream reach. When shaded stream reaches were exposed to full sunlight after the injection ended, photoreductive dissolution of iron oxide released sorbed 32P, which was then also removed downstream. The removal from the stream was modeled as a first-order process by using a reactive solute transport transient storage model. Concentrations of 32P mass-’ of algae were typically lo-fold greater than concentrations in hydrous iron oxides. During the injection, concentrations of 32P increased in the cellular P pool containing soluble, low-molecular-weight compounds and confirmed direct algal uptake of 32P0, from water. Mass balance calculations indicated that algal uptake and sorption on iron oxides were significant in removing phosphate. We conclude that in stream ecosystems, PO, sorbed by iron oxides can act as a dynamic nutrient reservoir regulated by photoreduction.

The relationship between soil color and iron oxide content in a surface-flow constructed wetland that successfully treats acid mine drainage (AMD) is examined with regard to its potential importance to wetland treatment of AMD. Twenty-one oxidized surficial soil samples (

Schwertmannite, a ferric oxyhydroxysulfate mineral typically found under acidic, high sulfate and iron aqueous conditions, such as acid mine drainage environments, was studied using analytical high resolution transmission electron microscopy (HRTEM). HRTEM offers advantages over bulk techniques such as powder x-ray diffraction and pair distribution function (PDF) analysis of synchrotron data, in its ability to discern multiple phases within poorly crystalline nanominerals. Based on extensive HRTEM observations of both natural and synthetic schwertmannite samples, the authors suggest that schwertmannite should not be described as a single phase mineral with a repeating unit cell, but as a polyphasic nanomineral with crystalline areas spanning less than a few nanometers within an amorphous matrix. The few visible lattice fringes observable in both natural and synthetic schwertmannite agree well with d-spacings of goethite (and jarosite in natural samples) implying that the transformation from schwertmannite to these phases occurs as a gradual structural reordering at the nanoscale. In the synthetic study, the complete transformation from schwertmannite to goethite nanorods and nanoparticles within 24 hours at 75°C was observed, indicating a low energetic barrier to schwertmannite's phase transformation. We also found that amorphous silica can be intimately entrained within natural schwertmannite, and that high concentrations of arsenic can be held in close association of nanocrystalline regions of the mineral. Ph. D.

The behaviour of Fe, Cu and Zn, added to the upper Tambo River (Victoria, Australia) via a metal-enriched groundwater input, was studied during a period of very low river flow. Water samples were collected over a 1.3-km section of the river located immediately downstream of the spring input. Heavy metals were separated into three fractions (dissolved, colloidal and particulate) using tangential flow filtration. Within the ‘input region’, the pH was low (5.1–5.8) and sulphate (306–359 mg L–1), total Fe (2.81 mg L–1), total Cu (19.7 mg L–1) and total Zn (24.1 mg L–1) concentrations all increased significantly. Subsequently, the total metal concentrations reduced with distance downstream of the input, and approached values similar to those recorded upstream of the input region at the end of the study region. Most of the Fe was oxidised before it entered the river as a thick hydrous iron oxide floc that travelled downstream close to the riverbed. The remaining dissolved Fe (mainly Fe(II)) that entered the river largely controlled the behaviour of Cu and Zn in the ‘active region’ (75–400 m). This Fe(II) was rapidly oxidised to Fe(III), which then removed large amounts of the dissolved Cu (65%) and Zn (55%) into the colloidal fraction. Processes such as settling of particles, dilution by groundwater inputs and sorption of dissolved Cu and Zn onto sediments removed the remainder of the Cu and Zn.

Two acid mine drainage streams have been investigated by detailed analysis of their sediments and waters, to obtain an understanding of the dominant processes which control the transport and attenuation of heavy metals under conditions of chronic high-level pollutant input. One of the water-courses has a thick hydrous iron oxide crust on its bed, where biotically mediated oxidation of ferrous iron resulted in precipitation of amorphous ferric hydroxide, along with substantial quantities of adsorbed silica, sulphate and Al and lesser quantities of As. Small amounts of K and Pb (and possibly hydronium) jarosites were also present in the sediments. Changes in pH and in the concentrations of Cu, Zn, and Cd appear to be mainly the result of dilution by seeps and tributaries. Although no sediment was recovered during collection of water samples from the second stream, saturation index calculations imply that precipitation should have been occurring. The observed down-stream loss of a number of elements supported this conclusion. The solids predicted to be precipitating were A1(OH) 3 , Cu 2 (OH) 2 CO 3 , and Fe(OH) 3 . Observed decreases in the concentrations of Cd, Zn and Mn can be accounted for on the basis of dilution alone. However, the additional mechanism of neutralization by higher pH inflows is required to account for the decrease in hydrogen ion concentration downstream. The basis for a potentially useful new technique (congruent element analysis) which enables the identification of conservative components in streams is presented. Comparison of logarithmic concentration versus distance plots delineates the point where chemical removal mechanisms become important for each element.

A variety of iron oxides were identified by X-ray diffraction in sediments receiving acid drainage from mine tailing and coal refuse impoundments. Small amounts of goethite and hematite were found in the sediment samples. However, the major iron oxide species was ferrihydrite which gave diffuse diffraction bands at angles corresponding to d = 2.5, 2.2 and 1.5A. Main core line binding energies in Fe (2p) and O (1s) X-ray photoelectron spectra were consistent with the hydrous nature and predominance of ferrihydrite. Electron microscopy and energy-dispersive X-ray spectroscopy also showed that individual bacterial cells promoted the development of iron oxide mineralization. The bacterial associated iron oxides were similar to those in the bulk sediment samples, and exhibited structures conforming to the presence of chemisorbed sulfate or silicate anions.