Formation Of Iron Sulfides Research Articles

New Alkylether-Thiazolium Room-Temperature Ionic Liquid Lubricants: Surface Interactions and Tribological Performance.

The use of newly synthesized alkylether-thiazolium ionic liquids as lubricants is described for the first time. Two ionic liquids composed of a thiazolium cation and a bis(trifluoromethanesulfonyl)amide ([Th][Tf2N]) or dicyanamide ([Th][(NC)2N]) anion have been studied, and their tribological behavior has been compared with that of 1-butyl-3-methylimidazolium bis(trifluoromethanesulfonyl)amide ([Im][Tf2N]) in pin-on-disk tests using sapphire balls against AISI 52100 or AISI 316L steels. All ionic liquids show higher contact angles on AISI 316L steel than on AISI 52100, the lowest values found for ([Im][Tf2N]) on both steel surfaces. AISI 52100 shows similar friction coefficients for all lubricants, and negligible wear rates for the ionic liquids containing the bis(trifluoromethanesulfonyl)amide anion. Immersion tests show no corrosion of AISI 52100 in imidazolium or thiazolium bis(trifluoromethanesulfonyl)amide ionic liquids. AISI 316L shows similar friction coefficients for both bis(trifluoromethanesulfonyl)amide ionic liquids, but the lowest wear rate is obtained for [Th][Tf2N]. An increase in friction coefficient and wear rate is observed for thiazolium dicyanamide. This increase is related to a tribocorrosion process due to decomposition of the thiazolium cation. XPS shows the formation of iron sulfide on the wear track on AISI 316L after lubrication with thiazolium dicyanamide. No tribocorrosion processes take place for the [Tf2N] ionic liquids.

Enhanced Dechlorination of 1,2-Dichloroethane by Coupled Nano Iron-Dithionite Treatment

1,2-Dichloroethane (1,2-DCA) is a chlorinated solvent classified as a probable human carcinogen. Due to its extensive use in industrial applications, widespread contamination, and recalcitrance toward abiotic dechlorination, 1,2-DCA remains a challenging compound for the remediation community. Over the past decade, nano zerovalent iron (nZVI) has been efficiently used to treat many of the chlorinated compounds of concern. However, thus far, even nZVI (monometallic or bimetallic) has been unable to dechlorinate 1,2-DCA. Therefore, an alternative treatment coupling nZVI with dithionite to treat 1,2-DCA is proposed in this work. Coupled nZVI-dithionite was able to degrade >90% 1,2-DCA over the course of a year. The effects of dithionite and nZVI loadings, carboxymethyl cellulose (CMC) coating, addition of palladium, and other iron species as metal surfaces on the degradation kinetics were also investigated. Observed pseudo-first-order rate constants (kobs) ranged from 3.8 × 10(-3) to 7.8 × 10(-3) d(-1). Both nucleophilic substitution and reductive dechlorination are the proposed mechanisms for 1,2-DCA degradation by coupled nZVI-dithionite treatment. Characterization analysis of the nZVI-dithionite nanoparticles shows that most of the iron was still preserved in the zerovalent state even after more than one year of reactivity with some iron sulfide (FeS) formation. Scanning electron microscopy (SEM) analysis shows that the nanosized spherical particles were still present along with the FeS platelets. This novel treatment represents the first nZVI-based formulation to achieve nearly complete degradation of 1,2-DCA.

Microbial sedimentary imprint on the deep Dead Sea sediment

AbstractA study of an International Continental Drilling Program core recovered from the middle of the modern Dead Sea has identified microbial traces within this subsurface hypersaline environment. A comparison with an active microbial mat exhibiting similar evaporative processes characterized iron‐sulphur mineralization and exopolymeric substances resulting from microbial activity. Exopolymeric substances were identified in the drilled sediment but unlike other hypersaline environments, it appears that they have a limited effect on the precipitation of calcium carbonate in the sedimentary column. Sulphate reduction, however, plays a role in all types of evaporative facies, leading to the formation of diagenetic iron sulphides in glacial and interglacial intervals. Their synthesis seems to occur under progressive sulphidation that generally stops at greigite because of incomplete sulphate reduction. The latter may be caused by a lack of suitable organic matter in this hypersaline, hence energy‐demanding, environment. Pyrite may be found in periods of high lake productivity, when more labile organic matter is available. The carbon and sulphur cycles are thus influenced by microbial activity in the Dead Sea environment and this influence results in diagenetic transformations in the deep sediment.

Environmental control on the occurrence of high-coercivity magnetic minerals and formation of iron sulfides in a 640 ka sediment sequence from Lake Ohrid (Balkans)

Abstract. The bulk magnetic mineral record from Lake Ohrid, spanning the past 637 kyr, reflects large-scale shifts in hydrological conditions, and, superimposed, a strong signal of environmental conditions on glacial–interglacial and millennial timescales. A shift in the formation of early diagenetic ferrimagnetic iron sulfides to siderites is observed around 320 ka. This change is probably associated with variable availability of sulfide in the pore water. We propose that sulfate concentrations were significantly higher before ∼ 320 ka, due to either a higher sulfate flux or lower dilution of lake sulfate due to a smaller water volume. Diagenetic iron minerals appear more abundant during glacials, which are generally characterized by higher Fe / Ca ratios in the sediments. While in the lower part of the core the ferrimagnetic sulfide signal overprints the primary detrital magnetic signal, the upper part of the core is dominated by variable proportions of high- to low-coercivity iron oxides. Glacial sediments are characterized by high concentration of high-coercivity magnetic minerals (hematite, goethite), which relate to enhanced erosion of soils that had formed during preceding interglacials. Superimposed on the glacial–interglacial behavior are millennial-scale oscillations in the magnetic mineral composition that parallel variations in summer insolation. Like the processes on glacial–interglacial timescales, low summer insolation and a retreat in vegetation resulted in enhanced erosion of soil material. Our study highlights that rock-magnetic studies, in concert with geochemical and sedimentological investigations, provide a multi-level contribution to environmental reconstructions, since the magnetic properties can mirror both environmental conditions on land and intra-lake processes.

Iron biogeochemistry in Holocene palaeo and actual salt marshes in coastal areas of the Pampean Plain, Argentina

In salt marshes, the hydrodynamics and the availability of iron, organic matter and sulphate, influence the formation and/or dissolution of iron sulfides and iron oxyhydroxides. Therefore, they constitute key factors affecting the iron biogeochemical processes in these environments. The aim of this work is to evaluate the physico-chemical and mineralogical variations associated to iron biogeochemistry in palaeo and actual salt marshes in the area of influence of the Mar Chiquita coastal lagoon, Pampean Plain, Argentina. In soils of exhumed palaeo marshes, the iron contents are 56–95 μmol g−1, whereas these contents decrease to 36–75 μmol g−1 in actual marsh soils. The presence of framboidal and poliframboidal pyrites associated with gypsum, barite, calcite, halite and iron oxyhydroxides defines the conditions of the pedosedimentary sequences of the Holocene paleomarshes. Sequences of pyrite formation (sulfidization) and degradation (sulfuricization) were observed. These processes were evidenced by a sequential extraction, reflecting that the largest proportion of iron is in the form of crystalline iron oxides (28–76 %) and lepidocrocite (6–16 %); while the proportion associated with ferrihydrite and pyrite is low (0–9 and 1–17 %, respectively). These facts could be partly explained by the complex redox processes characteristic of these environments, such as aeration generated by the rhizosphere and intense bioturbation by invertebrates. These iron biomineralizations have been useful because they allow paleoenvironmental interpretations and characterization of paleomarshes, and environmental inferences related to the management of actual salt marshes.

Sedimentary Sulphur:Iron Ratio Indicates Vivianite Occurrence: A Study from Two Contrasting Freshwater Systems.

An increasing number of studies constrain the importance of iron for the long-term retention of phosphorus (P) under anoxic conditions, i.e. the formation of reduced iron phosphate minerals such as vivianite (Fe3(PO4)2⋅8H2O). Much remains unknown about vivianite formation, the factors controlling its occurrence, and its relevance for P burial during early sediment diagenesis. To study the occurrence of vivianite and to assess its relevance for P binding, surface sediments of two hydrologically contrasting waters were analysed by heavy-liquid separation and subsequent powder X-ray diffraction. In Lake Arendsee, vivianite was present in deeper sediment horizons and not in the uppermost layers with a sharp transition between vivianite and non-vivianite bearing layers. In contrast, in lowland river Lower Havel vivianite was present in the upper sediment layers and not in deeper horizons with a gradual transition between non-vivianite and vivianite bearing layers. In both waters, vivianite occurrence was accompanied by the presence of pyrite (FeS2). Vivianite formation was favoured by an elevated iron availability through a lower degree of sulphidisation and was present at a molar ratio of total sulphur to reactive iron smaller than 1.1, only. A longer lasting burden of sediments by organic matter, i.e. due to eutrophication, favours the release of sulphides, and the formation of insoluble iron sulphides leading to a lack of available iron and to less or no vivianite formation. This weakening in sedimentary P retention, representing a negative feedback mechanism (P release) in terms of water quality, could be partly compensated by harmless Fe amendments.

Magnetic properties of surficial sediments in Lake Ogawara on the Pacific coast of northeastern Japan: spatial variability and correlation with brackish water stratification

To examine limnological conditions in Lake Ogawara on the Pacific coast of northwestern Japan, we investigated the magnetic properties of dredged bottom sediment originally collected from the lake in the summer of 2011. We used non-destructive methods to measure the low-field magnetic susceptibility shortly after sampling, and anhysteretic remanent magnetization (ARM) was assessed in 2012 and 2015. The ARM acquisition and demagnetization curves from littoral sites showed several patterns that reflect the provenance of the sediments. At water depths below 10 m, the magnetic susceptibility and ARM of greenish black mud with high organic content decreased considerably with the increase in water depth, but ARM increased slightly at water depths greater than 16 m. We also found that the magnetic concentrations of mud samples were reduced markedly during a period of storage for about 3 years. We attributed these reductions to diagenetic loss of magnetic minerals, which had been enhanced at deeper sites. It is possible that the ARM carriers in deeper areas were derived from authigenic formation of iron sulfide or from deposition of suspended matter in the hypolimnion water. We propose that the magnetic properties of surficial sediments are controlled by limnological stratification of the brackish lake water, thus possibly providing an analog for down-core variations of magnetic parameters associated with the modification of magnetic minerals during reductive diagenesis.

The influence of Fe(III) on oil biodegradation in excessively moistened soils and sediments

Soils are self-purified from oil slowly, in the north, in particular, where hydromorphic conditions and low temperatures hinder the process. Oxidation of oil hydrocarbons depends on the type of electron acceptors and decreases in the following sequence: denitrification > Mn4+ reduction > Fe3+ reduction > sulfate reduction > methanogenesis. Usually, not all of these redox reactions develop in contaminated excessively moistened soils and sediments. Fe(III) reduction and methanogenesis are the most common: the latter is manifested near the contamination source, while the former develops in less contaminated areas. Fe reduction hinders the methanogenesis. In oil-contaminated areas, Fe reduction is also combined with sulfate reduction, the latter intensifying Fe reduction due to the formation of iron sulfides. Concurrently with oil degradation in excessively moistened soils and sediments, the composition of iron compounds changes due to the increasing Fe(II) share magnetite, as well as siderite and ferrocalcite (in calcareous deposits), and iron sulfides (in S-containing medium) are formed.

Authigenesis of magnetic minerals in gas hydrate-bearing sediments in the Nankai Trough, offshore Japan

Gas hydrate occurrence is one of the possible mechanisms invoked for iron sulfide formation. A high-resolution rock magnetic study was conducted in IODP Expedition 316 Hole C0008C located in the Megasplay Fault Zone of the Nankai Trough, offshore Japan. In this particular zone, no bottom simulating reflectors (BSR), indicating the base of the gas hydrate stability field, have been identified. Two hundred and eighteen Pleistocene samples were collected from 70 to 110 m CSF in order to document the changes in the concentration, grain size, and rock magnetic parameters of magnetic minerals, through the gas hydrate-bearing horizons. Two different populations of magnetic grains are recognized in the pseudosingle domain range. Three types of magnetic mineral assemblages are identified: iron oxides (magnetite), ferrimagnetic iron sulfides (greigite and pyrrhotite), and their mixture. Greigite and pyrrhotite are authigenic and constitute six layers, called IS1–IS6. IS1, IS3, IS4, and IS6 are associated with pore water anomalies, suggesting the occurrence of gas hydrates and anoxic conditions. IS2 and IS5 are probable gas hydrates horizons, although there is no independent data to confirm it. The remaining intervals are mainly composed of detrital iron oxides and paramagnetic iron sulfides. Two scenarios based on different diagenetic stages are proposed to explain the variations in the magnetic properties and mineralogy over the studied interval. The results suggest that rock magnetism appears useful to better constrain the gas hydrate distribution in Hole C0008C, and counterbalances the low resolution of pore water analyses and the absence of a BSR.

Effect of some Sulphur Additives on the Degradation of 9Cr-1Mo Steel after its 10 Years Service in the CCR Platforming Unit

The work shows the results of the tests of 9Cr-1Mo steel, which was for 10 years operated in the CCR platforming unit in Group Lotos SA in Gdańsk, and then in the laboratory was sulphidised during 166 h at a temperature of 600 °C. Sulphidation was performed in a mixture of H2-H2S gases at the vapour pressure of sulphur 4.1·10-14 atm, so the order of magnitude of vapour pressure was less than that of the dissociation pressure of FeS. Although sulphidising took place in conditions which preclude any iron sulphide formation, research results have demonstrated that after 166 hour exposure in reaction mixture in 9Cr-1Mo steel produces iron and chromium sulfides. Sulphide precipitates form under a layer of fine carbides, located directly on the surface of steel. Formation of scale sulphide here is most likely caused by the penetration of hydrogen sulphide through the porous layer of carbides that increases the pressure of hydrogen sulphide. Thus the vapour of sulphur in apertures and narrow passages occurs between the layer of carbides and the rest of oversaturated carbon layer top, until its pressure value is reached allowing the formation of sulphide scaling.

Application of a long-lasting colloidal substrate with pH and hydrogen sulfide control capabilities to remediate TCE-contaminated groundwater

A long-lasting emulsified colloidal substrate (LECS) was developed for continuous carbon and nanoscale zero-valent iron (nZVI) release to remediate trichloroethylene (TCE)-contaminated groundwater under reductive dechlorinating conditions. The developed LECS contained nZVI, vegetable oil, surfactants (Simple Green™ and lecithin), molasses, lactate, and minerals. An emulsification study was performed to evaluate the globule droplet size and stability of LECS. The results show that a stable oil-in-water emulsion with uniformly small droplets (0.7μm) was produced, which could continuously release the primary substrates. The emulsified solution could serve as the dispensing agent, and nZVI particles (with diameter 100–200nm) were distributed in the emulsion evenly without aggregation. Microcosm results showed that the LECS caused a rapid increase in the total organic carbon concentration (up to 488mg/L), and reductive dechlorination of TCE was significantly enhanced. Up to 99% of TCE (with initial concentration of 7.4mg/L) was removed after 130 days of operation. Acidification was prevented by the production of hydroxide ion by the oxidation of nZVI. The formation of iron sulfide reduced the odor from produced hydrogen sulfide. Microbial analyses reveal that dechlorinating bacteria existed in soils, which might contribute to TCE dechlorination.

The effect of temperature on carbon steel corrosion under geological conditions

We investigated the role of temperature on the carbon steel corrosion under simulated geological conditions. To simulate the effect of temperature increase due to radioactive decay, we conducted batch experiments using Callovo-Oxfordian (COx) claystone and synthetic water formation with steel coupons at 30°C and 90°C for 6months. The corrosion products have been studied by scanning electron microscope/energy dispersive X-ray spectroscopy, X-ray diffraction and micro-Raman spectroscopy. At 30°C, experiments showed the formation of magnetite and iron sulphide, indicating the activation of sulphate-reducing bacteria. At 90°C a continuous iron sulphide layer was identified on steel surface due to the reduction by hydrogen of pyrite originating from claystone into pyrrhotite and hydrogen sulphide. Thus, sulphide production may occur even in the absence of microbial activity at high temperature and must be taken into consideration regarding the near-field geochemical evolution.

Effect of Oxygen Content in a Tank Gas Space with Sulfurous Oil on the Rate of Pyrophoric Deposit Formation and Chemical Composition

Creation of a nitrogen atmosphere within a tank gas space with sulfurous oil leads to a reduction in steel corrosion rate and pyrophoric deposit formation rate. A reduction in oxygen content in the gas phase to a level of 3 vol.% or less makes it possible to avoid pyrophoric iron sulfide formation.

Sulfide Stress Cracking and Electrochemical Corrosion of Precipitation Hardening Steel After Plasma Oxy-Nitriding

In this paper, we present the results of a duplex plasma nitriding followed by an oxidizing stage process (which is also referred as oxy-nitriding) on the corrosion behavior of a 17-4PH precipitation hardening stainless steel. The formation of both, expanded martensite (b.c.t. α′N-phase) and chromium oxide (type Cr2O3) in the subsurface of oxy-nitrided samples at specific controlled conditions, leads in a noticeable increasing in the time-to-rupture during the sulfide stress cracking test, in comparison with an untreated reference sample. Oxy-nitriding improves the corrosion performance of the alloy when it is immersed in solutions saturated by sour gas, which extends the application potential of this type of steel in the oil and gas extraction and processing industry. The presence of the oxy-nitrided layer inhibits the corrosion process that occurs in the near-surface region, where hydrogen is liberated after the formation of iron sulfides, which finally produces a fragile fracture by micro-crack propagation; the obtained results suggest that oxy-nitriding slows this process, thus delaying the rupture of the specimen. Moreover, oxy-nitriding produces a hard, sour gas-resistant surface, but do not significantly affect the original chloride ion solution resistance of the material.

Technology Focus: Oilfield Chemistry (September 2014)

Technology Focus Sulfide scales are becoming more prevalent in the oilfield environment. There are several reasons for this, including higher-pressure and -temperature fields being developed, which can be associated with the formation of zinc and lead sulfide; fields maturing, with iron sulfide being often associated with old mature waterflooded fields; and sour production becoming more commonplace, resulting in more-challenging integrity management. Little comprehensive research has been conducted on sulfide scales when compared to that concerning conventional carbonate- and sulfate-scale species. Perhaps this is partly because of the challenge of studying these materials in the laboratory and the perception that iron sulfide formation in the oil field is protective of tubulars and production equipment. As the prevalence of these scales increases, so too does the focus being placed on them by the industry, academia, and independent research groups. However, a lot of space remains for innovation and understanding. Today, the correct mitigation and cleanup methods can be selected most appropriately only on the basis of accurate root-cause-of-failure analysis. Generally, no single solution can be applied to all systems because the root causes differ from system to system. Commonality exists, however, insofar as a combination of dissolver/chelant and surfactant is nearly always needed for cleanup of the typically oil-wet scale. Control methods have focused very much on indirect techniques of removing one of the scaling species, such as chelation and sequestration of either the metal cation or the sulfide in order to reduce supersaturation. However, as the formation environments become more severe, these methods are being found to be increasingly challenging as they typically involve stoichiometric amounts of preventive chemicals. More recently, however, threshold inhibitors are starting to be reported in the literature, including some very promising chemistry evaluations from several research groups. Critical to success here is the accurate testing in the laboratory that best approximates field conditions. Unlike with conventional scale types, this is very easy to get wrong, so great care must be taken when intending to realize conformity between laboratory testing and success in the field. One thing is certain: More work needs to be performed by the industry before it can be said that control of these scales is understood and is as easy to manage as it is for conventional scale species. JPT

Sulfidization of lepidocrocite and its effect on uranium phase distribution and reduction

Sulfidization of iron oxyhydroxides can be accompanied by a release of adsorbed uranium, thus enhancing the mobility of uranium in systems undergoing a shift in redox conditions. We investigated the phase distribution and redox state of uranium in batch experiments, in which lepidocrocite with adsorbed U(VI) was reacted with sulfide. The amount of added sulfide was varied in the experiments performed, at pH 8 and ionic strength of 0.1M. Sulfide, when not added in excess, was removed from solution within less than 1h of reaction time. Consumption of dissolved sulfide was accompanied by reduction of Fe(III) and formation of iron sulfide. Each addition of sulfide led to an instantaneous release of uranium into solution. This release is most likely caused by the exchange of hydroxide groups at the lepidocrocite surface by thiol groups which have a lower tendency to bind uranium. Along with the consumption of dissolved sulfide, part of the released uranium became reassociated with the solid phase. This can be explained by a reversal of the ligand exchange process at the solid surfaces. However, steady state concentrations of dissolved uranium remained higher than before sulfide addition, indicating that the product of lepidocrocite sulfidization has a lower affinity for uranium than the starting material. Reduction of U(VI) also contributed to the transfer of dissolved uranium back to the solid phase. X-ray absorption spectroscopy revealed that reduction of U(VI) occurred in all experiments. The extent of U(VI) reduction depended on sulfide addition, however, formation of UO2 occurred within a period of 48h only when sulfide was added in excess. This suggests that the presence of dissolved sulfide is a prerequisite for fast reduction of U(VI) and formation of UO2. This would imply that the fast reaction of lepidocrocite with sulfide outcompetes reduction of U(VI) and, by this, kinetically inhibits the thermodynamically more favorable reduction of U(VI) to uraninite. Our results demonstrate that the transition from oxic to sulfidic conditions can lead to intermittent mobilization of uranium which is not expected based on equilibrium thermodynamics.

Factors controlling spatial distributions and relationships of carbon, nitrogen, phosphorus and sulphur in sediments of the stratified and eutrophic Gulf of Gdansk

Spatial distribution and coupling of carbon, nitrogen, phosphorus and sulphur were studied in sediments of the Gulf of Gdansk, southern Baltic Sea. We report data on sedimentary contents of total and organic carbon (TC and OC), total nitrogen (TN), total and organic phosphorus (TP and OP) and total sulphur (TS), as well as pore water concentrations of ammonium, phosphate and hydrogen sulphide. The lowest values of all the investigated parameters were observed in coastal area, while the highest were noted in sediments below halocline which is attributed to changing hydrodynamic conditions and sedimentation regimes with depth. The contents of TC, OC, TN, TP, OP and TS in sediments and their molar ratios were also noted to vary spatially in relation to distance from land and oxygen conditions in near-bottom water. As a result of high organic matter supply to the sediments caused by eutrophication we observed increased contents of TC, OC, TN, TP and OP in the upper few centimetres of sediment. Results obtained for the Gdansk Deep indicate that sediments in this area are site of accumulation of sulphur and redox-dependent phosphorus release.We analysed relationships between the investigated parameters and organic matter content in sediments measured as loss-on-ignition (LOI). Regression analysis indicated that LOI was a good estimator of contents of OC, TN and OP in the Gulf of Gdansk sediments and may be used as a screening tool when planning geochemical investigations. However, calculated equations can only be applied to LOI results obtained at similar temperature and exposure time (550°C, 6h). In addition to this, the method was unreliable for prediction of TS content in euxinic environments where, as in the Gdansk Deep sediments, accumulation of sulphur occurs due to the formation of iron (II) sulphides.

Rock-magnetic signature of precipitation and extreme runoff events in south-eastern Patagonia since 51,200 cal BP from the sediments of Laguna Potrok Aike

A 106-m long sediment sequence from the maar lake Laguna Potrok Aike in southern Patagonia was recovered in the framework of the International Continental Scientific Drilling Program (ICDP) Potrok Aike maar lake Sediment Archive Drilling prOject (PASADO). About half of the sedimentary sequence is composed of mass movement deposits (MMDs) and the event-corrected record reaches back to 51,200 cal BP. Here we present a high-resolution rock-magnetic study revealing two sedimentary facies associated with MMDs and characterized by two different types of spurious gyroremanent magnetization (GRM) acquired during static alternating field demagnetization. The first rock-magnetic signature is detected in MMDs composed of reworked sand and tephra material. The signature consists of GRM acquired during demagnetization of the natural remanent magnetization (NRM) and other rock-magnetic properties typical of iron sulfides such as greigite. We interpret these intervals as authigenic formation of iron sulfides in suboxic conditions within the MMD. The second rock-magnetic signature consists of a series of 10 short intervals located on the top of MMDs characterized by GRM acquisition during demagnetization of the isothermal remanent magnetization (IRM). Based on geological, limnological, stratigraphic and climatic evidence these layers are interpreted as reflecting pedogenic hematite and/or goethite brought to the lake by runoff events related to precipitation and permafrost melt. The pedogenic iron minerals mobilized from the catchment most likely settled out of suspension on top of MMDs after a rapid remobilization event. The series of runoff events corresponds to periods of increased lacustrine productivity in Laguna Potrok Aike and are coeval within the limit of the chronology to warm periods of the Last Glacial as recorded in Antarctica, the deglaciation in the mid-latitudes of the Southern Hemisphere and enhanced precipitation during the Early Holocene in southeastern Patagonia.

Microbially-accelerated consolidation of oil sands tailings. Pathway II: solid phase biogeochemistry

Consolidation of clay particles in aqueous tailings suspensions is a major obstacle to effective management of oil sands tailings ponds in northern Alberta, Canada. We have observed that microorganisms indigenous to the tailings ponds accelerate consolidation of mature fine tailings (MFT) during active metabolism by using two biogeochemical pathways. In Pathway I, microbes alter porewater chemistry to indirectly increase consolidation of MFT. Here, we describe Pathway II comprising significant, direct and complementary biogeochemical reactions with MFT mineral surfaces. An anaerobic microbial community comprising Bacteria (predominantly Clostridiales, Synergistaceae, and Desulfobulbaceae) and Archaea (Methanolinea/Methanoregula and Methanosaeta) transformed FeIII minerals in MFT to amorphous FeII minerals during methanogenic metabolism of an added organic substrate. Synchrotron analyses suggested that ferrihydrite (5Fe2O3. 9H2O) and goethite (α-FeOOH) were the dominant FeIII minerals in MFT. The formation of amorphous iron sulfide (FeS) and possibly green rust entrapped and masked electronegative clay surfaces in amended MFT. Both Pathways I and II reduced the surface charge potential (repulsive forces) of the clay particles in MFT, which aided aggregation of clays and formation of networks of pores, as visualized using cryo-scanning electron microscopy (SEM). These reactions facilitated the egress of porewater from MFT and increased consolidation of tailings solids. These results have large-scale implications for management and reclamation of oil sands tailings ponds, a burgeoning environmental issue for the public and government regulators.

Iron isotopes in an Archean ocean analogue

Iron isotopes have been extensively used to trace the history of microbial metabolisms and the redox evolution of the oceans. Archean sedimentary rocks display greater variability in iron isotope ratios and more markedly negative values than those deposited in the Proterozoic and Phanerozoic. This increased variability has been linked to changes in either water column iron cycling or the extent of benthic microbial iron reduction through time. We tested these contrasting scenarios through a detailed study of anoxic and ferruginous Lac Pavin (France), which can serve as a modern analogue of the Archean ocean. A depth-profile in the water column of Lac Pavin shows a remarkable increase in dissolved Fe concentration (0.1–1200μM) and δ56Fe values (−2.14‰ to +0.31‰) across the oxic–anoxic boundary to the lake bottom. The largest Fe isotope variability is found at the redox boundary and is related to partial oxidation of dissolved ferrous iron, leaving the residual Fe enriched in light isotopes. The analysis of four sediment cores collected along a lateral profile (one in the oxic layer, one at the redox boundary, one in the anoxic zone, and one at the bottom of the lake) indicates that bulk sediments, porewaters, and reactive Fe mostly have δ56Fe values near 0.0±0.2‰, similar to detrital iron. In contrast, pyrite δ56Fe values in sub-chemocline cores (60, 65, and 92m) are highly variable and show significant deviations from the detrital iron isotope composition (δ56Fepyrite between −1.51‰ and +0.09‰; average −0.93‰). Importantly, the pyrite δ56Fe values mirror the δ56Fe of dissolved iron at the redox boundary—where near quantitative sulfate and sulfide drawdown occurs—suggesting limited iron isotope fractionation during iron sulfide formation. This finding has important implications for the Archean environment. Specifically, this work suggests that in a ferruginous system, most of the Fe isotope variability observed in sedimentary pyrites can be tied to water column cycling—foremost to the oxidation of dissolved ferrous iron. This supports previous suggestions that enhanced iron isotope variability in the Archean may record a unique stage in Earth’s history where partial ferrous iron oxidation in upwelling water masses was a common process, probably linked to oxygenic or anoxygenic photosynthesis.