Ferric Iron Minerals Research Articles

Authigenic albite formation due to water–rock interactions — Case study: Magnus oilfield (UK, Northern North Sea)

It is the aim of this contribution to test whether organic–inorganic interactions could induce the formation of authigenic albite. This concept and related results are being compared with modelling scenarios which are purely based on inorganic geochemical reactions. In order to unravel the pathway of authigenic albite formation, this paper presents results of a multidisciplinary study from imaging, geochemistry, mineralogy, and hydrogeochemical modelling. The Jurassic reservoir sandstones of the Magnus oilfield (UK, North Sea) were chosen as a test site.Albite occurs with 4–18wt.% in the Magnus sandstones and its contents vary with depth. However, albite contents increase with increasing K-feldspar contents and decreasing grain size. It occurs in three forms: (1) as lamellae in perthite, (2) as overgrowth on/in corroded feldspar, and, (3) as cloudy replacing albite patches in K-feldspar. The albite overgrowth has the highest chemical purity (100% albite) whilst albite lamellae and replacing albite patches are slightly less pure (containing 1–4% anorthite). Albite appears non-altered, and has a euhedral morphology and dull cathodoluminescence. It commonly co-occurs with corroded K-feldspar grains.The precipitation of diagenetic albite in the Magnus sandstones is attributed to deep burial 80Ma ago and may have continued until today at temperatures between 90–120°C. The results of hydrogeochemical modelling offer two possible pathways for the authigenic albite formation: (1) Dissolution of unstable minerals (such as kaolinite and chalcedony) coupled to reduction of ferric iron minerals by products generated during oil generation, migration and degradation; (2) Dissolution of non-end member feldspar, such as K-feldspar with 10% albite, coupled to illite formation can account for trace amounts of albite due to an elevated Na+/K+ activity ratio in the pore water.

The Archean Nickel Famine Revisited.

Iron formations (IF) preserve a history of Precambrian oceanic elemental abundance that can be exploited to examine nutrient limitations on early biological productivity. However, in order for IF to be employed as paleomarine proxies, lumped-process distribution coefficients for the element of interest must be experimentally determined or assumed. This necessitates consideration of bulk ocean chemistry and which authigenic ferric iron minerals controlled the sorption reactions. It also requires an assessment of metal mobilization reactions that might have occurred in the water column during particle descent and during post-depositional burial. Here, we summarize recent developments pertaining to the interpretation and fidelity of the IF record in reconstructions of oceanic trace element evolution. Using an updated compilation, we reexamine and validate temporal trends previously reported for the nickel content in IF (see Konhauser et al., 2009 ). Finally, we reevaluate the consequences of methanogen Ni starvation in the context of evolving views of the Archean ocean-climate system and how the Ni famine may have ultimately facilitated the rise in atmospheric oxygen.

Diverse arsenic- and iron-cycling microbial communities in arsenic-contaminated aquifers used for drinking water in Bangladesh.

Subsurface removal of arsenic by injection with oxygenated groundwater has been proposed as a viable technology for obtaining 'safe' drinking water in Bangladesh. While the oxidation of ferrous iron to solid ferric iron minerals, to which arsenic adsorbs, is assumed to be driven by abiotic reactions, metal-cycling microorganisms may potentially affect arsenic removal. A cultivation-independent survey covering 24 drinking water wells in several geographical regions in Bangladesh was conducted to obtain information on microbial community structure and diversity in general, and on specific functional groups capable of the oxidation or reduction of arsenic or iron. Each functional group, targeted by either group-specific 16S rRNA or functional gene amplification, occurred in at least 79% of investigated samples. Putative arsenate reducers and iron-oxidizing Gallionellaceae were present at low diversity, while more variation in potentially arsenite-oxidizing microorganisms and iron-reducing Desulfuromonadales was revealed within and between samples. Relations between community composition on the one hand and hydrochemistry on the other hand were in general not evident, apart from an impact of salinity on iron-cycling microorganisms. Our data suggest widespread potential for a positive contribution of arsenite and iron oxidizers to arsenic removal upon injection with oxygenated water, but also indicate a potential risk for arsenic re-mobilization by anaerobic arsenate and iron reducers once injection is halted.

Biomining in reverse gear: Using bacteria to extract metals from oxidised ores

Biomining, as traditionally practised, uses aerobic, acidophilic microorganisms to accelerate the oxidative dissolution of sulfide minerals present in ores and concentrates, thereby either causing target metals to be solubilised (e.g. copper) or made accessible to chemical extraction (e.g. gold). Many acidophiles are also able to catalyse the dissimilatory reduction of ferric iron in anoxic or oxygen-depleted environments, and can accelerate the reductive dissolution of ferric iron minerals, such as goethite, under such conditions. Recent work has demonstrated how this approach can be used to extract metals (nickel, copper, cobalt and manganese) from oxidised ores, such as laterites deposits, at low (∼30°C) temperatures. Reductive mineral dissolution has been trialled successfully with a variety of ores, pointing to a generic application of this approach.

Fe-oxide grain coatings support bacterial Fe-reducing metabolisms in 1.7-2.0 km-deep subsurface quartz arenite sandstone reservoirs of the Illinois Basin (USA).

The Cambrian-age Mt. Simon Sandstone, deeply buried within the Illinois Basin of the midcontinent of North America, contains quartz sand grains ubiquitously encrusted with iron-oxide cements and dissolved ferrous iron in pore-water. Although microbial iron reduction has previously been documented in the deep terrestrial subsurface, the potential for diagenetic mineral cementation to drive microbial activity has not been well studied. In this study, two subsurface formation water samples were collected at 1.72 and 2.02 km, respectively, from the Mt. Simon Sandstone in Decatur, Illinois. Low-diversity microbial communities were detected from both horizons and were dominated by Halanaerobiales of Phylum Firmicutes. Iron-reducing enrichment cultures fed with ferric citrate were successfully established using the formation water. Phylogenetic classification identified the enriched species to be related to Vulcanibacillus from the 1.72 km depth sample, while Orenia dominated the communities at 2.02 km of burial depth. Species-specific quantitative analyses of the enriched organisms in the microbial communities suggest that they are indigenous to the Mt. Simon Sandstone. Optimal iron reduction by the 1.72 km enrichment culture occurred at a temperature of 40°C (range 20–60°C) and a salinity of 25 parts per thousand (range 25–75 ppt). This culture also mediated fermentation and nitrate reduction. In contrast, the 2.02 km enrichment culture exclusively utilized hydrogen and pyruvate as the electron donors for iron reduction, tolerated a wider range of salinities (25–200 ppt), and exhibited only minimal nitrate- and sulfate-reduction. In addition, the 2.02 km depth community actively reduces the more crystalline ferric iron minerals goethite and hematite. The results suggest evolutionary adaptation of the autochthonous microbial communities to the Mt. Simon Sandstone and carries potentially important implications for future utilization of this reservoir for CO2 injection.

Acidibacter ferrireducens gen. nov., sp. nov.: an acidophilic ferric iron-reducing gammaproteobacterium.

An acidophilic gammaproteobacterium, isolated from a pit lake at an abandoned metal mine in south-west Spain, was shown to be distantly related to all characterized prokaryotes, and to be the first representative of a novel genus and species. Isolate MCF85 is a Gram-negative, non-motile, rod-shaped mesophilic bacterium with a temperature growth optimum of 32-35 °C (range 8-45 °C). It was categorized as a moderate acidophile, growing optimally at pH 3.5-4.0 and between pH 2.5 and 4.5. Under optimum conditions its culture doubling time was around 75 min. Only organic electron donors were used by MCF85, and the isolate was confirmed to be an obligate heterotroph. It grew on a limited range of sugars (hexoses and disaccharides, though not pentoses) and some other small molecular weight organic compounds, and growth was partially or completely inhibited by small concentrations of some aliphatic acids. The acidophile grew in the presence of >100 mM ferrous iron or aluminium, but was more sensitive to some other metals, such as copper. It was also much more tolerant of arsenic (V) than arsenic (III). Isolate MCF85 catalysed the reductive dissolution of the ferric iron mineral schwertmannite when incubated under micro-aerobic or anaerobic conditions, causing the culture media pH to increase. There was no evidence, however, that the acidophile could grow by ferric iron respiration under strictly anoxic conditions. Isolate MCF85 is the designated type strain of the novel species Acidibacter ferrireducens (=DSM 27237(T) = NCCB 100460(T)).

Extraction of copper from an oxidized (lateritic) ore using bacterially catalysed reductive dissolution

An oxidized lateritic ore which contained 0.8 % (by weight) copper was bioleached in pH- and temperature-controlled stirred reactors under acidic reducing conditions using pure and mixed cultures of the acidophilic chemolithotrophic bacterium Acidithiobacillus ferrooxidans. Sulfur was provided as the electron donor for the bacteria, and ferric iron present in goethite (the major ferric iron mineral present in the ore) acted as electron acceptor. Significantly more copper was leached by bacterially catalysed reductive dissolution of the laterite than in aerobic cultures or in sterile anoxic reactors, with up to 78 % of the copper present in the ore being extracted. This included copper that was leached from acid-labile minerals (chiefly copper silicates) and that which was associated with ferric iron minerals in the lateritic ore. In the anaerobic bioreactors, soluble iron in the leach liquors was present as iron (II) and copper as copper (I), but both metals were rapidly oxidized (to iron (III) and copper (II)) when the reactors were aerated. The number of bacteria added to the reactors had a critical role in dictating the rate and yield of copper solubilised from the ore. This work has provided further evidence that reductive bioprocessing, a recently described approach for extracting base metals from oxidized deposits, has the potential to greatly extend the range of metal ores that can be biomined.

Characterization of exopolymeric substances (EPS) produced by Aeromonas hydrophila under reducing conditions

The aim of this work was to investigate the production of extracellular polymeric substances (EPS) by Aeromonas hydrophila grown under anaerobic conditions. EPS composition was studied for planktonic cells, cells attached to carbon fibre supports using a soluble ferric iron source and cells grown with a solid ferric iron mineral (gossan). Conventional spectrophotometric methods, Fourier transform infrared (FTIR) and confocal laser scanning microscopy (CLSM) were used to determine the main components in the biofilm extracted from the cultures. The key EPS components were proteins, indicating their importance for electron transfer reactions. Carbohydrates were observed mostly on the mineral and contained terminal mannosyl and/or terminal glucose, fucose and N-acetylgalactosamine residues.

Ecotoxicological characteristic of a soil polluted by radioactive elements and heavy metals before and after its bioremediation

Cinnamonic soils from southeastern Bulgaria are heavily polluted with radionuclides (uranium, radium) and toxic heavy metals (copper and lead) due to the aerial transportation of fine particles from flotation tailing dumps to the soil surface. As a result of this, the polluted soils are characterized by a slightly alkaline pH (7.82) and positive net neutralization potential (+136.8kgCaCO3⁄t). A fresh sample of cinnamonic soil was subjected to remediation under laboratory conditions in four lysimeters each containing 70kg of soil. The preliminary study revealed that most of the pollutants were presented as carbonate, reducible and oxidizable fractions, i.e. pollutant ions were specifically adsorbed by carbonate and ferric iron minerals or were capsulated in sulfides. The applied soil treatment was connected with the leaching of the pollutants located mainly in the horizon A, their transportation through the soil profile as soluble forms, and their precipitation in the rich-in-clay subhorizon B3. The efficiency of leaching depended on the activity of the indigenous microflora and on the chemical processes connected with the solubilization of pollutants and formation of stable complexes with some organic compounds and chloride and hydrocarbonate ions. These processes were considerably enhanced by adding hay to the horizon A and irrigating the soil with water solutions containing the above-mentioned ions and some nutrients. After 18months of treatment, each of the soil profiles in the different lysimeters was divided into five sections reflecting the different soil layers. The soil in these sections was subjected to a detailed chemical analysis and the data obtained were compared with the relevant data obtained before the start of the experiment. The best leaching of pollutants from horizon A was measured in the variants where soil mulching was applied. For example, the best leaching of lead (54.5%) was found in the variant combining this technique and irrigation with solutions containing only nutrients. The best leaching of uranium (66.3%), radium (62.5%), and copper (15.1%) was measured in the variant in which the soil was subjected to mulching and irrigation with alkaline solutions containing hydrocarbonate ions. Despite the removal of higher amounts of these pollutants from the soil, the acute soil toxicity towards earthworms (Lumbricus terrestris) was higher in comparison to the toxicity of soil that had been treated in other variants. Furthermore, the highly alkaline soil pH (10.47) that was determined through the applied alkaline leaching resulted in an acute soil toxicity to oats (Avena sativa) and clover (Trifolium repens) that was even higher in comparison to the toxicity of the non-treated soil. These data revealed that the soil detoxification was depended not only on the decrease of the total concentration and on the bioavailable forms of the above-mentioned pollutants but also on the changes that had taken place in chemical and geotechnical properties of the treated soil.

Acidocella aromatica sp. nov.: an acidophilic heterotrophic alphaproteobacterium with unusual phenotypic traits

Three obligately heterotrophic bacterial isolates were identified as strains of a proposed novel species of extremely acidophilic, mesophilic Alphaproteobacteria, Acidocella aromatica. They utilized a restricted range of organic substrates, which included fructose (but none of the other monosaccharides tested), acetate and several aromatic compounds (benzoate, benzyl alcohol and phenol). No growth was obtained on complex organic substrates, such as yeast extract and tryptone. Tolerance of the proposed type strain of the species (PFBC) to acetic acid was much greater than that typically reported for acidophiles. The bacteria grew aerobically, and catalyzed the dissimilatory reductive dissolution of the ferric iron mineral schwertmannite under both micro-aerobic and anaerobic conditions. Strain PFBC did not grow anaerobically via ferric iron respiration, though it has been reported to grow in co-culture with acid-tolerant sulfidogenic bacteria under strictly anoxic conditions. Tolerance of strains of Acidocella aromatica to nickel were about two orders of magnitude greater than those of other Acidocella spp., though similar levels of tolerance to other metals tested was observed. The use of this novel acidophile in solid media designed to promote the isolation and growth of other (aerobic and anaerobic) acidophilic heterotrophs is discussed.

A New Direction for Biomining: Extraction of Metals by Reductive Dissolution of Oxidized Ores

Biomining, the biotechnology that uses microorganisms to extract metals from ores and concentrates, is currently used exclusively for processing reduced ores and mine wastes. Metals of economic value also occur extensively in oxidized ores, such as nickel laterites. While these are not amenable to oxidative dissolution, the ferric iron minerals they contain can, in theory, be disrupted by iron reduction, causing associated metals to be released. We have harnessed the ability of the facultatively anaerobic, acidophilic bacterium Acidithiobacillus ferroooxidans to couple the oxidation of elemental sulphur to the reduction of ferric iron in the goethite fraction of a limonitic nickel ore at 30 °C. Nickel and other metals (Co, Cr and Mn) were effectively solubilised and maintained in solution due to the low pH (1.8) of the leach liquor. The results highlight the potential for the bioprocessing of oxidized, iron-rich ores using an approach that is energy-saving and environmentally-benign compared with metallurgical processes currently applied to the extraction of Ni from lateritic ores.

Biomining: an Established and Dynamic Biotechnology

“Biomining” is generic term to describe the application of living organisms to extract and recover metals from mineral ores and waste materials. Since its inception as a crude technology (“dump leaching”) for treating “run of mine” rocks and boulders that contained too little copper to be processed by conventional processing, engineering options used in biomining have become increasingly refined and diverse. Currently, microbiological processing is used to extract both base metals (copper, and to lesser extents nickel and zinc) and precious metals (mostly gold) from ores and mineral concentrates in heaps and stirred-tank bioreactors, as well as in dumps. Recent developments include the demonstration, at pilot-scale, of indrect leaching of zinc sulfide concentrates, in which the biological step (regeneration of ferric iron) is carried out independently of abiotic mineral oxidation, and using microbiologically-mediated reductive dissolution of ferric iron minerals to liberate nickel from lateritic ores.

Mapping the distribution of ferric iron minerals on a vertical mine face using derivative analysis of hyperspectral imagery (430–970 nm)

Hyperspectral imagery is used to map the distribution of iron and separate iron ore from shale (a waste product) on a vertical mine face in an open-pit mine in the Pilbara, Western Australia. Vertical mine faces have complex surface geometries which cause large spatial variations in the amount of incident and reflected light. Methods used to analyse imagery must minimise these effects whilst preserving any spectral variations between rock types and minerals. Derivative analysis of spectra to the 1st-, 2nd- and 4th-order is used to do this. To quantify the relative amounts and distribution of iron, the derivative spectrum is integrated across the visible and near infrared spectral range (430–970nm) and over those wavelength regions containing individual peaks and troughs associated with specific iron absorption features. As a test of this methodology, results from laboratory spectra acquired from representative rock samples were compared with total amounts of iron minerals from X-ray diffraction (XRD) analysis. Relationships between derivatives integrated over the visible near-infrared range and total amounts (% weight) of iron minerals were strongest for the 4th- and 2nd-derivative (R2=0.77 and 0.74, respectively) and weakest for the 1st-derivative (R2=0.56). Integrated values of individual peaks and troughs showed moderate to strong relationships in 2nd- (R2=0.68–0.78) and 4th-derivative (R2=0.49–0.78) spectra. The weakest relationships were found for peaks or troughs towards longer wavelengths.The same derivative methods were then applied to imagery to quantify relative amounts of iron minerals on a mine face. Before analyses, predictions were made about the relative abundances of iron in the different geological zones on the mine face, as mapped from field surveys. Integration of the whole spectral curve (430–970nm) from the 2nd- and 4th-derivative gave results which were entirely consistent with predictions. Conversely, integration of the 1st-derivative gave results that did not fit with predictions nor distinguish between zones with very large and small amounts of iron oxide.Classified maps of ore and shale were created using a simple level-slice of the 1st-derivative reflectance at 702, 765 and 809nm. Pixels classified as shale showed a similar distribution to kaolinite (an indicator of shales in the region), as mapped by the depth of the diagnostic kaolinite absorption feature at 2196nm. Standard statistical measures of classification performance (accuracy, precision, recall and the Kappa coefficient of agreement) indicated that nearly all of the pixels were classified correctly using 1st-derivative reflectance at 765 and 809nm. These results indicate that data from the VNIR (430–970nm) can be used to quantify, without a priori knowledge, the total amount of iron minerals and to distinguish ore from shale on vertical mine faces.

Redox Transformations of Iron at Extremely Low pH: Fundamental and Applied Aspects

Many different species of acidophilic prokaryotes, widely distributed within the domains Bacteria and Archaea, can catalyze the dissimilatory oxidation of ferrous iron or reduction of ferric iron, or can do both. Microbially mediated cycling of iron in extremely acidic environments (pH < 3) is strongly influenced by the enhanced chemical stability of ferrous iron and far greater solubility of ferric iron under such conditions. Cycling of iron has been demonstrated in vitro using both pure and mixed cultures of acidophiles, and there is considerable evidence that active cycling of iron occurs in acid mine drainage streams, pit lakes, and iron-rich acidic rivers, such as the Rio Tinto. Measurements of specific rates of iron oxidation and reduction by acidophilic microorganisms show that different species vary in their capacities for iron oxido-reduction, and that this is influenced by the electron donor provided and growth conditions used. These measurements, and comparison with corresponding data for oxidation of reduced sulfur compounds, also help explain why ferrous iron is usually used preferentially as an electron donor by acidophiles that can oxidize both iron and sulfur, even though the energy yield from oxidizing iron is much smaller than that available from sulfur oxidation. Iron-oxidizing acidophiles have been used in biomining (a technology that harness their abilities to accelerate the oxidative dissolution of sulfidic minerals and thereby facilitate the extraction of precious and base metals) for several decades. More recently they have also been used to simultaneously remediate iron-contaminated surface and ground waters and produce a useful mineral by-product (schwertmannite). Bioprocessing of oxidized mineral ores using acidophiles that catalyze the reductive dissolution of ferric iron minerals such as goethite has also recently been demonstrated, and new biomining technologies based on this approach are being developed.

The behavior of arsenic and antimony at Pezinok mining site, southwestern part of the Slovak Republic

Arsenic and antimony contamination is found at the Pezinok mining site in the southwest of the Slovak Republic. Investigation of this site included sampling and analysis of water, mineralogical analyses, sequential extraction, in addition to flow and geochemical modeling. The highest dissolved arsenic concentrations correspond to mine tailings (up to 90,000 μg/L) and the arsenic is present predominately as As(V). The primary source of the arsenic is the dissolution of arsenopyrite. Concentration of antimony reaches 7,500 μg/L and its primary source is the dissolution of stibnite. Pore water in mine tailings is well-buffered by the dissolution of carbonates (pH values between 6.6 and 7.0) and arsenopyrite grains are surrounded by reaction rims composed of ferric iron minerals. Based on sequential extraction results, most solid phase arsenic is in the reducible fraction (i.e. ferric oxyhydroxides), sulfidic fraction, and residual fraction. Distribution of antimony in the solid phase is similar, but contents are lower. The principal attenuation mechanism for As(V) is adsorption to ferric oxide and hydroxides, but the adsorption seems to be limited by the competition with Sb(V) produced by the oxidation of stibnite for adsorption sites. Water in mine tailings is at equilibrium with gypsum and calcite, but far from equilibrium with any arsenic and antimony minerals. The concentrations of arsenic and antimony in the surrounding aquifer are much lower, with maximum values of 215 and 426 μg/L, respectively. Arsenic and antimony are transported by ground water flow towards the Blatina Creek, but their loading from ground water to the creek is much lower compared with the input from the mine adits. In the Blatina Creek, arsenic and antimony are attenuated by dilution and by adsorption on ferric iron minerals in stream sediments with resulting respective concentrations of 93 and 45 μg/L at the site boundary south of mine tailing ponds.

Paleo-redox fronts and their formation in carbonate mound sediments from the Rockall Trough

Piston cores from the summits of coral topped carbonate mounds at the south west Rockall Trough margin reveal that the sediments have undergone significant post-depositional modifications affecting the original geochemical signature and mineralogical composition of the sediments. This diagenetic imprint provides information about the geochemical processes within cold-water coral mounds. The most prominent result of diagenetic alteration of the primary sediment composition is the absence or poor preservation of aragonitic coral skeletons in certain depth intervals associated with lithification. This study focuses on the enrichment of redox-sensitive elements and the dissolution of primary magnetic ferric iron minerals in the depth interval below lithification levels. By combining the magnetic susceptibility with the XRF signal of Fe and Ti specifically, intervals with susceptibility variations related to the conversion of strongly magnetic into weakly magnetic iron species can be defined. In all three studied cores a succession is recognised with a lithified interval with aragonite dissolution and low-Mg calcite precipitates that is underlain by an interval of magnetite dissolution and of iron and manganese enrichment. For the most recent lithified interval it is demonstrated that initial lithification occurred before an erosional regime was in place, most likely near the end of interglacial or at the start of glacial periods.

Reductive dissolution of ferric iron minerals: A new approach for bio-processing nickel laterites

Nickel laterites represent the major ore reserves of this base metal present in the lithosphere. However, processing these ores by conventional technologies involves considerable energy or reagent expenditure and consequently is less cost-effective than extracting nickel from sulfide ores. Biological options, using metal-complexing organic acids and mineral acids generated by fungi and bacteria, have been investigated but generally found to be ineffective in terms of extraction dynamics or yields. We have examined the possibility of using bacteria that can bring about the reductive dissolution of ferric iron minerals and thereby facilitate the extraction of nickel from a lateritic ore at relatively low (<30–45 °C) temperatures. Four species of iron-reducing acidophilic bacteria were screened for their abilities to solubilise nickel from a limonitic laterite ore in which the major iron mineral present was goethite. One of these ( Acidithiobacillus ferrooxidans) was selected for further study only the basis of it being able to use a cost-effective energy source (elemental sulfur) to mediate the dissolution of goethite at mildly acidic conditions (pH < 2). Cultures were set up in 2 L bioreactors, maintained at pH 1.8 (±0.1) and 30 °C, and initially aerated (to promote growth of the bacteria on sulfur) and then switched to anaerobic conditions when nickel laterite ore (crushed to <6 mm, with a nickel grade of 0.5%) was added. Over 70% of the nickel present in the ore was solubilised within 14 days, and solubilised metals remained in solution due to the low pH of the leachate. In contrast, only 10% of the nickel was solubilised (by non-reductive acid dissolution) when the cultures were continuously aerated. The results suggest that biological processing of limonitic nickel laterites is technically feasible and, more generically, that reductive dissolution can be used to bioprocess ferric oxide mineral ores.

Does Iron Cycling Trigger Generation of Acidity in Groundwaters of Western Australia?

In large areas of Western Australia, acidic groundwaters occur with pH values distinctly lower than 3, generation of which has been attributed to the oxidation of Fe(II). Incubation experiments performed with sediments from playas receiving acid groundwater demonstrated occurrence of reductive dissolution of ferric iron minerals at rates [670 nmol (g reactive iron)(-1) h(-1)] similar to those observed in sediments of acidic mining lakes (AML), indicating thatthe pH was established through an acidity-driven iron cycle in analogy to processes occurring in AML systems. The low pH values observed in acidic groundwaters and AML, however, can only be achieved if the anion corresponding to Fe(III) is that of a strong acid. In AML, sulfate is derived from pyrite oxidation. Because this process is reported not to occur in the acidic groundwater systems of Western Australia, we have derived a conceptual model according to which sulfate is generated upon reaction of weathering-derived alkalinity with gypsum to form calcite, which is abundant in these areas. The model proposes that part of the alkalinity generated during weathering is stared as calcite in the landscape, which leads to spatial separation of acidity and alkalinity.

Visible–Near Infrared Point Spectrometry of Drill Core Samples from Río Tinto, Spain: Results from the 2005 Mars Astrobiology Research and Technology Experiment (MARTE) Drilling Exercise

Sampling of subsurface rock may be required to detect evidence of past biological activity on Mars. The Mars Astrobiology Research and Technology Experiment (MARTE) utilized the Río Tinto region, Spain, as a Mars analog site to test dry drilling technologies specific to Mars that retrieve subsurface rock for biological analysis. This work examines the usefulness of visible-near infrared (VNIR) (450-1000 nm) point spectrometry to characterize ferric iron minerals in core material retrieved during a simulated Mars drilling mission. VNIR spectrometry can indicate the presence of aqueously precipitated ferric iron minerals and, thus, determine whether biological analysis of retrieved rock is warranted. Core spectra obtained during the mission with T1 (893-897 nm) and T2 (644-652 nm) features indicate goethite-dominated samples, while relatively lower wavelength T1 (832-880 nm) features indicate hematite. Hematite/goethite molar ratios varied from 0 to 1.4, and within the 880-898 nm range, T1 features were used to estimate hematite/goethite molar ratios. Post-mission X-ray analysis detected phyllosilicates, which indicates that examining beyond the VNIR (e.g., shortwave infrared, 1000-2500 nm) will enhance the detection of other minerals formed by aqueous processes. Despite the limited spectral range of VNIR point spectrometry utilized in the MARTE Mars drilling simulation project, ferric iron minerals could be identified in retrieved core material, and their distribution served to direct core subsampling for biological analysis.

Effect of Sorbed Fe(II) on the Initial Reduction Kinetics of 6-Line Ferrihydrite and Amorphous Ferric Phosphate by Shewanella putrefaciens

Incomplete utilization of reactive ferric iron minerals by dissimilatory iron-reducing bacteria has been ascribed to inhibition by adsorption of Fe2 + to the mineral or bacterial surfaces. We tested this hypothesis by monitoring the reduction of 6-line ferrihydrite and amorphous ferric phosphate by Shewanella putrefaciens for up to 50 hours, at circumneutral pH and in the presence of excess electron donor. The microbial iron reduction incubations were performed with Fe(III) substrates or bacteria that had been exposed beforehand to solutions containing dissolved Fe2 + (range: 0–500 μ M) for relatively short durations (≤12 hours). The reduction rates were not, or only weakly, affected by pre-sorbed Fe2 +. A slight decrease in the reduction rate was observed for ferric phosphate particles whose ferrozine-extractable Fe2 + concentrations approached the estimated mineral surface site density. Thus, under the range of experimental conditions considered here, sorbed Fe2+ did not limit the transfer of electrons from membrane-bound reductases to Fe(III) centers at the mineral surface. We hypothesize that adsorption of Fe2 + inhibits the initial Fe(III) reduction kinetics only when the surface sites of the mineral surface, or the metal binding sites in the bacterial cell wall, are (nearly) all saturated with Fe2 +.