Reactive Iron Minerals Research Articles

Reviews and syntheses: Iron – a driver of nitrogen bioavailability in soils?

Abstract. An adequate supply of bioavailable nitrogen (N) is critical to soil microbial communities and plants. Over the last decades, research efforts have rarely considered the importance of reactive iron (Fe) minerals in the processes that produce or consume bioavailable N in soils compared to other factors such as soil texture, pH, and organic matter (OM). However, Fe is involved in both enzymatic and non-enzymatic reactions that influence the N cycle. More broadly, reactive Fe minerals restrict soil organic matter (SOM) cycling through sorption processes but also promote SOM decomposition and denitrification in anoxic conditions. By synthesizing available research, we show that Fe plays diverse roles in N bioavailability. Fe affects N bioavailability directly by acting as a sorbent, catalyst, and electron transfer agent or indirectly by promoting certain soil features, such as aggregate formation and stability, which affect N turnover processes. These roles can lead to different outcomes in terms of N bioavailability, depending on environmental conditions such as soil redox shifts during wet–dry cycles. We provide examples of Fe–N interactions and discuss the possible underlying mechanisms, which can be abiotic or microbially meditated. We also discuss how Fe participates in three complex phenomena that influence N bioavailability: priming, the Birch effect, and freeze–thaw cycles. Furthermore, we highlight how Fe–N bioavailability interactions are influenced by global change and identify methodological constraints that hinder the development of a mechanistic understanding of Fe in terms of controlling N bioavailability and highlight the areas of needed research.

Stabilization of mineral-associated organic carbon in Pleistocene permafrost

Ice-rich Pleistocene-age permafrost is particularly vulnerable to rapid thaw, which may quickly expose a large pool of sedimentary organic matter (OM) to microbial degradation and lead to emissions of climate-sensitive greenhouse gases. Protective physico-chemical mechanisms may, however, restrict microbial accessibility and reduce OM decomposition; mechanisms that may be influenced by changing environmental conditions during sediment deposition. Here we study different OM fractions in Siberian permafrost deposited during colder and warmer periods of the past 55,000 years. Among known stabilization mechanisms, the occlusion of OM in aggregates is of minor importance, while 33-74% of the organic carbon is associated with small, <6.3 µm mineral particles. Preservation of carbon in mineral-associated OM is enhanced by reactive iron minerals particularly during cold and dry climate, reflected by low microbial CO2 production in incubation experiments. Warmer and wetter conditions reduce OM stabilization, shown by more decomposed mineral-associated OM and up to 30% higher CO2 production. This shows that considering the stability and bioavailability of Pleistocene-age permafrost carbon is important for predicting future climate-carbon feedback.

Storm-driven variations in depositional environments modify pyrite sulfur isotope records

The sulfur isotopic composition of marine pyrite (δ34Spyr) is one of the major geochemical tools to reconstruct global changes in Earth's surface environment. Storm-driven variations in depositional environments, however, can play key roles in modifying the δ34Spyr signal. Here we present δ34Spyr values in a complete Holocene muddy storm deposit on the East China coastal plain, which is identified by comprehensive analyses of sediment components, organic matter composition, bulk organic carbon isotopic ratios, carbon and oxygen isotopic ratios of carbonates and trace element concentrations. We find that positive (+5.8‰ to +15.8‰) and negative (−9.0‰ to −19.7‰) δ34Spyr values were preserved in two successive intervals of the muddy storm deposit (ca. 62 cm long), corresponding to the high-energy storm peak phase (HESPP) and the waning-energy late storm phase (WELSP), respectively. We propose that the 34S enrichment in pyrite from the HESPP is most likely due to a combination of storm reworking of sediments and high sedimentation rates, which involves various physical and chemical processes leading to the accumulation of 34S-enriched pyrite, such as oxidation of near-surface sulfides, reduced exchange of sulfate between sediment pore fluids and the overlying water column, and/or input of excess reactive iron minerals. In contrast, lower sedimentation rates and limited sedimentary remobilization during the WELSP allow the isotopic signal of early-formed 32S-enriched pyrite to be preserved. The striking shift in δ34Spyr values, therefore, reflects a dramatic change in the local depositional environment between the HESPP and WELSP, suggesting that non-steady-state deposition induced by storm activity facilitates the formation of isotopically “heavy” pyrite. This sharp shift can be further generalized as a characteristic feature of δ34Spyr values in storm deposits. Our work highlights the critical impact of weather- and climate-event-driven depositional variations on δ34Spyr values, adding to the growing evidence emphasizing the local environmental and diagenetic controls on these records.

Degradation of chlorinated solvents with reactive iron minerals in subsurface sediments from redox transition zones.

Reactive iron (Fe) mineral coatings found in subsurface reduction-oxidation transition zones (RTZs) contribute to the attenuation of contaminants. An 18.3-m anoxic core was collected from the site, where constituents of concern (COCs) in groundwater included chlorinated solvents. Reactive Fe mineral coatings were found to be abundant in the RTZs. This research focused on evaluating reaction kinetics with anoxic sediments bearing ferrous mineral nano-coatings spiked with either tetrachloroethylene (PCE), trichloroethylene (TCE), or 1,4-dichlorobenzene (1,4-DCB). Reaction kinetics with RTZ sediments followed pseudo-first-order reactions for the three contaminants with 90% degradation achieved in less than 39 days. The second-order rate constants for the three COCs ranged from 6.20×10-4 to 1.73×10-3 Lg-1h-1 with pyrite (FeS2), 4.97×10-5 to 1.24×10-3 Lg-1h-1with mackinawite (FeS), 1.25×10-4 to 1.89×10-4 Lg-1h-1 with siderite (FeCO3), and 1.79×10-4 to 1.10×10-3 Lg-1h-1 with magnetite (Fe3O4). For these three chlorinated solvents, the trend for the rate constants followed: Fe(II) sulfide minerals >magnetite >siderite. The high reactivity of Fe mineral coatings is hypothesized to be due to the large surface areas of the nano-mineral coatings. As a result, these surfaces are expected to play an important role in the attenuation of chlorinated solvents in contaminated subsurface environments.

Iron Reduction in Profundal Sediments of Ultraoligotrophic Lake Tahoe under Oxygen-Limited Conditions.

Increased periods of bottom water anoxia in deep temperate lakes due to decreasing frequency and depth of water column mixing in a warming climate may result in the reductive dissolution of iron minerals and increased flux of nutrients from the sediment into the water column. Here, we assessed the sediment properties and reactivities under depleted oxygen concentrations of Lake Tahoe, a deep ultraoligotrophic lake in the Sierra Nevada mountain range. Using whole-core incubation experiments, we found that a decrease in dissolved oxygen concentration in the top 2 cm of the sediment resulted in an extension of the microbial iron reduction zone from below 4.5 to below 1.5 cm depth. Concentrations of reactive iron generally decreased with sediment depth, and microbial iron reduction seemingly ceased as concentrations of Fe(II) approximated concentrations of reactive iron. These findings suggest that microorganisms preferentially utilized reactive iron and/or iron minerals became less reactive due to mineral transformation and surface passivation. The estimated release of iron mineral-associated phosphorus is not expected to change Lake Tahoe's trophic state but will likely contribute to increased phytoplankton productivity if mixed into surface waters.

Microbial iron cycling during palsa hillslope collapse promotes greenhouse gas emissions before complete permafrost thaw

Reductive dissolution during permafrost thaw releases iron-bound organic carbon to porewaters, rendering previously stable carbon vulnerable to microbial decomposition and subsequent release to the atmosphere. How mineral iron stability and the microbial processes influencing mineral dissolution vary during transitional permafrost thaw are poorly understood, yet have important implications for carbon cycling and emissions. Here we determine the reactive mineral iron and associated organic carbon content of core extracts and porewaters along thaw gradients in a permafrost peatland in Abisko, Sweden. We find that iron mineral dissolution by fermentative and dissimilatory iron(III) reduction releases aqueous Fe2+ and aliphatic organic compounds along collapsing palsa hillslopes. Microbial community analysis and carbon emission measurements indicate that this release is accompanied by an increase in hydrogenotrophic methanogen abundance and methane emissions at the collapsing front. Our findings suggest that dissolution of reactive iron minerals contributes to carbon dioxide and methane production and emission, even before complete permafrost thaw.

Seasonal Fluctuations in Iron Cycling in Thawing Permafrost Peatlands.

In permafrost peatlands, up to 20% of total organic carbon (OC) is bound to reactive iron (Fe) minerals in the active layer overlying intact permafrost, potentially protecting OC from microbial degradation and transformation into greenhouse gases (GHG) such as CO2 and CH4. During the summer, shifts in runoff and soil moisture influence redox conditions and therefore the balance of Fe oxidation and reduction. Whether reactive iron minerals could act as a stable sink for carbon or whether they are continuously dissolved and reprecipitated during redox shifts remains unknown. We deployed bags of synthetic ferrihydrite (FH)-coated sand in the active layer along a permafrost thaw gradient in Stordalen mire (Abisko, Sweden) over the summer (June to September) to capture changes in redox conditions and quantify the formation and dissolution of reactive Fe(III) (oxyhydr)oxides. We found that the bags accumulated Fe(III) under constant oxic conditions in areas overlying intact permafrost over the full summer season. In contrast, in fully thawed areas, conditions were continuously anoxic, and by late summer, 50.4 ± 12.8% of the original Fe(III) (oxyhydr)oxides were lost via dissolution. Periodic redox shifts (from 0 to +300 mV) were observed over the summer season in the partially thawed areas. This resulted in the dissolution and loss of 47.2 ± 20.3% of initial Fe(III) (oxyhydr)oxides when conditions are wetter and more reduced, and new formation of Fe(III) minerals (33.7 ± 8.6% gain in comparison to initial Fe) in the late summer under more dry and oxic conditions, which also led to the sequestration of Fe-bound organic carbon. Our data suggest that there is seasonal turnover of iron minerals in partially thawed permafrost peatlands, but that a fraction of the Fe pool remains stable even under continuously anoxic conditions.

Cryoturbation impacts iron-organic carbon associations along a permafrost soil chronosequence in northern Alaska

In permafrost soils, substantial amounts of organic carbon (OC) are potentially protected from microbial degradation and transformation into greenhouse gases by association with reactive iron (Fe) minerals. As permafrost environments respond to climate change, increased drainage of thaw lakes in permafrost regions is predicted. Soils will subsequently develop on these drained thaw lakes, but the role of Fe-OC associations in future OC stabilization during this predicted soil development is unknown. To fill this knowledge gap, we have examined Fe-OC associations in organic, cryoturbated and mineral horizons along a 5500-year chronosequence of drained thaw lake basins in Utqiaġvik, Alaska. By applying chemical extractions, we found that ∼17% of the total OC content in cryoturbated horizons is associated with reactive Fe minerals, compared to ∼10% in organic or mineral horizons. As soil development advances, the total stocks of Fe-associated OC more than double within the first 50 years after thaw lake drainage, because of increased storage of Fe-associated OC in cryoturbated horizons (from 8 to 75% of the total Fe-associated OC stock). Spatially-resolved nanoscale secondary ion mass spectrometry showed that OC is primarily associated with Fe(III) (oxyhydr)oxides which were identified by 57Fe Mössbauer spectroscopy as ferrihydrite. High OC:Fe mass ratios (>0.22) indicate that Fe-OC associations are formed via co-precipitation, chelation and aggregation. These results demonstrate that, given the proposed enhanced drainage of thaw lakes under climate change, OC is increasingly incorporated and stabilized by the association with reactive Fe minerals as a result of soil formation and increased cryoturbation.

A quantification of the effect of diagenesis on the paleoredox record in mid-Proterozoic sedimentary rocks

Abstract Iron speciation in ancient sedimentary rocks is widely used to reconstruct oceanic redox conditions over geological time, specifically to assess the extent of oxic, euxinic (anoxic containing sulfide), and ferruginous (anoxic containing iron) conditions. We explore how post-depositional sedimentary processes can skew particular geochemical signals in the rock record. One such process is when aqueous sulfide—including that produced in the sediment column—reacts with sedimentary iron, converting non-sulfide, highly reactive iron minerals to iron-sulfide minerals; this can lead to increased preservation of iron as pyrite and an overestimation of seafloor euxinia. We show that sedimentary rocks with higher (&amp;gt;5 wt%) total iron content are more buffered to this effect and thus are a more reliable indicator of true water-column euxinia. When considering this effect in the geological past, we estimate that true euxinia in the mid-Proterozoic may have been as much as fourfold less than previously thought—more in line with other recent paleoredox proxies not based on iron minerals. Marine iron and sulfate concentrations were more equivalent in Proterozoic–Neoproterozoic oceans, suggesting this time period was particularly susceptible to this post-depositional alteration, explaining the extent of euxinia suggested for this geological interval.

A chemical weathering control on the delivery of particulate iron to the continental shelf

The delivery of potentially reactive iron minerals to the marine environment exerts a major control on ocean and marine sediment biogeochemistry, including the preservation and burial of organic carbon. One aspect of the global iron cycle that has received little attention concerns the phase partitioning of iron in highly chemically-weathered sediments from (sub)tropical mountainous regions, where the sediment is commonly deposited directly onto adjacent continental margins. Here, we report the phase partitioning of particulate iron in surface seafloor sediments deposited from oxic bottom waters along the east coast of China, including the Bohai Sea, Yellow Sea and East China Sea, in addition to the continental shelf region adjacent to the (sub)tropical mountainous island of Hainan in the northern South China Sea. We document highly reactive (FeHR) to total iron (FeT) ratios for the Bohai Sea, Yellow Sea and East China Sea that are typical of global marine sediments deposited under oxic water column conditions. By contrast, FeHR/FeT ratios in Hainan offshore sediments are significantly elevated above normal oxic marine sediments. These Hainan offshore sediments display a strong positive correlation between FeHR/FeT ratios and the chemical index of alteration (CIA) weathering proxy, suggesting that the Fe speciation systematics are controlled by the intensity of chemical weathering. This observation is supported by additional geochemical data and Nd isotope analyses, which suggest a common source lithology for all the studied regions. The Hainan sediments thus document a specific scenario, whereby highly chemically weathered sediments from the mountainous Hainan region bypass the inner shore settings that commonly disproportionately trap Fe (oxyhydr)oxide minerals, depositing high concentrations of FeHR on the adjacent continental margin. Such enrichments likely aid in the preservation of organic carbon in marine sediments, suggesting that organic carbon preservation and burial may be enhanced by elevated FeHR in such settings. We also establish a set of essential criteria for potential recognition of chemical weathering-induced enrichments in FeHR/FeT ratios in ancient marine sediments.

Laboratory and initial field testing of the Min‐Trap™ for tracking reactive iron sulfide mineral formation during in situ remediation

AbstractThe Mineral Trap, or Min‐Trap™, is a monitoring well‐based sampler designed to collect direct physical evidence of reactive mineral formation in situ without collecting soil or rock core samples. The Min‐Trap consists of a nonreactive granular medium (e.g., silica sand) within water‐permeable mesh pillows that are supported inside a slotted polyvinyl chloride housing that is incubated within a conventional monitoring well. The primary objective of the Min‐Trap in this application is to collect reactive minerals that are forming in the aquifer in a retrievable format that can be submitted for laboratory analysis. To evaluate the capability of Min‐Traps to capture reactive iron minerals, both a laboratory tank test and a field test were conducted. Both tests confirmed that iron sulfide minerals form in the Min‐Trap under sulfate reducing conditions within several weeks. Analysis of the precipitated minerals via the AMIBA analysis suite showed that they almost entirely consisted of weak acid soluble (biogenic, microcrystalline) ferrous iron‐based minerals, and at least two thirds of the sulfur‐containing minerals were monosulfides (i.e., mackinawite) at the end of each test. Scanning electron microscopy confirmed the colocation of iron and sulfur in the mineral masses. The dominance of the ferrous iron and reduced sulfur verifies that little to no oxidation of the captured minerals occurred between sample collection and analysis. A subsurface soil core was collected during the field test next to the Min‐Trap‐containing well. AMIBA results were consistent between the native soil and the Min‐Trap except for much higher strong acid soluble (crystalline) ferric iron in the native soil when compared to the silica sand of the Min‐Trap, as expected. This work shows that Min‐Traps are useful for documenting the formation of reactive iron sulfides (FeSx) that can form during in situ anaerobic biostimulation and can drive complementary abiotic treatment of chlorinated volatile organic compounds. Mineralogical data obtained from Min‐Traps can be applied to assess remedial objectives at several stages of the remedial program, including initial characterization, alternatives evaluation, feasibility testing, remedy optimization, and transition from active treatment to passive remedial methods.

Ferrihydrite Reduction Increases Arsenic and Uranium Bioavailability in Unsaturated Soil.

Redox driven mobilization and plant uptake of contaminants under transiently saturated soil conditions need to be clarified to ensure food and water quality across different irrigation systems. We postulate that solid-phase iron reduction in anoxic microsites present in the rhizosphere of unsaturated soil is a key driver for mobilization and bioavailability of contaminants under nonflooded irrigation. To clarify this, two major crops, corn and soybean differing in iron uptake strategies, were grown in irrigated synthetic soil under semiarid conditions with gravimetric moisture content ∼12.5 ± 2.4%. 2-line ferrihydrite, which was coprecipitated with uranium and arsenic, served as the only iron source in soil. Irrespective of crop type, reduced iron was detected in pore water and postexperiment rhizosphere soil confirming ferrihydrite reduction. These results support the presence of localized anoxic microsites in the otherwise aerobic porous bulk soil causing reduction of ferrihydrite and concomitant increase in plant uptake of comobilized contaminants. Our findings indicate that reactive iron minerals undergo reductive dissolution inside anoxic microsites of primarily unsaturated soil, which may have implications on the mobility of trace element contaminants such as arsenic and uranium in irrigated unsaturated soils, accounting for 55% of the irrigated area in the US.

Phosphorus speciation in cultivated organic soils revealed by P K‐edge XANES spectroscopy

AbstractCultivated organic soils make a significant contribution to phosphorus (P) leaching losses from agricultural land, despite occupying a small proportion of cultivated area. However, less is known about P mobilisation processes and the P forms present in peat soils compared with mineral soils. In this study, P forms and their distribution with depth were investigated in two cultivated Histosol profiles, using a combination of wet chemical extraction and P K‐edge X‐ray absorption near‐edge structure (XANES) spectroscopy.Both profiles had elevated P content in the topsoil, amounting to around 40 mmol kg−1, and P speciation in both profiles was strongly dominated by organic P. Topsoils were particularly rich in organic P (P‐org), with relative proportions of up to 80%. Inorganic P in the profiles was almost exclusively adsorbed to surface reactive aluminium (Al) and iron (Fe) minerals. In one of the pro‐files, small contributions of Ca‐phosphates were detected.A commonly used P saturation index (PSI) based on ammonium‐oxalate extraction indicated a low to moderate risk of P leaching from both profiles. However, the capacity of soil Al and Fe to retain P in organic soils could be reduced by high competition from organic compounds for sorption sites. This is not directly accounted for in PSI and similar indices.Accumulation of P‐org in the topsoil may be attributable by microbial peat decomposition and transformation of mineral fertiliser P by both microbiota and crops. Moreover, high carbon–phosphorus ratio in the surface peat material in both profiles suggests reduced net mineralisation of P‐org in the two soils. However, advancing microbial peat decomposition will eventually lead to complete loss of peat horizons and to mineralisation of P‐org. Hence, P‐org in both profiles represents a huge potentially mobilised P pool.

The use of operationally-defined sequential Fe extraction methods for mineralogical applications: A cautionary tale from Mössbauer spectroscopy

Reactive iron minerals are crucial components of global nutrient cycles, directly controlling carbon transport and storage in marine sediments. Sequential selective extraction is frequently used for quantitatively characterising, and chemically isolating, individual Fe mineral phases. Reagent-specific mineral solubility is fundamental to the success of any sequential extraction, but is strongly affected by the varying physical and chemical morphology intrinsic to natural mineral samples. Natural sediment, rock, and soil samples often contain a mineral mixture, which further modifies solvent efficacy. 57Fe Mössbauer spectroscopy only probes the hyperfine interactions between next-nearest neighbouring atomic nuclei in the crystal lattice and is less affected by variation in mineral grain size and crystallinity than conventional, X-ray-based methods. In this study, we used Mössbauer spectroscopy in a novel context to cross-calibrate and optimise a popular, but frequently misused, sequential Fe extraction protocol. Our results showed that incomplete and premature removal of the target Fe minerals could occur at nearly every stage of the extraction and, in many cases, the leachate Fe content did not represent the target phase at all. Crystalline, natural siderite and amorphous, synthetic goethite were detected in the Mössbauer spectrum of the ammonium oxalate extraction for magnetite, after which all reactive Fe minerals should have been removed. Consistent with previous studies, and unlike many other clay minerals, nontronite was extracted as part of the highly reactive Fe pool, and in fact our data indicate that this mineral was extracted by the initial Na-acetate extraction that targets ‘carbonate-bound Fe’. Matrix effects appeared to cause variable yield efficiencies: synthetic goethite was successfully removed when present as an individual mineral yet persisted beyond its target extraction when present in an Fe mineral mixture. Although suitable for the quantification of operationally-defined Fe pools, we caution the unverified use of sequential Fe extraction protocols for mineral specific applications. The application of sequential Fe extractions to define the reactive Fe pools as a paleoredox proxy of depositional conditions appears relatively robust. The premature removal of 2-line ferrihydrite observed in this study (due to the use of the more aggressive Na-acetate extraction for crystalline siderite), does not limit the quantitative use of the sequential Fe extraction in ancient sediments, where such ‘easily reducible’ oxides are unlikely to persist. In contrast, attributing the outcomes of operationally-defined Fe pools to specific Fe minerals is precarious and potentially entirely erroneous. Where Fe mineral specificity or separation is required, we recommend post-extraction validation by another secondary technique. Mössbauer spectroscopy offers such a method that can independently verify extraction stages and assess mineral specificity.

R&amp;D Efforts of CSIR-IMMT Toward Solving Some Issues Related to Aluminum Production

Due to the rapid increase in aluminum production from high-grade bauxite ores, such reserves are fast depleting. Determining cost-effective processes for the treatment of low-grade bauxitic ores, utilization of different wastes and byproducts of aluminum industries, and improvement in the extraction process steps are some of the pertinent issues. Red mud, i.e., bauxite residue, is a serious threat to the environment that needs serious attention for its end use. Another issue is the effective utilization of fly ash generated in the captive power plant. This presentation covers some of the R&D efforts made by CSIR-IMMT such as (1) bauxite beneficiation process to remove reactive silica and iron minerals, (2) recovery of Al2O3 and other value-added products from fly ash, (3) utilization of bauxite residue to manufacture of bricks, (4) producing boehmite and gibbsite from Bayer’s liquor by means of organic additives, and (5) producing value-added Al-based chemicals from Al dross.

The role of iron oxides in the preservation of soil organic matter under long-term fertilization

The aim of this paper is to enlighten the role of highly reactive iron (Fe) minerals in soil organic carbon (SOC) preservation in soil aggregates. The effects of four long-term (37-year) fertilization regimes (NPK, chemical fertilization; NPKM, chemical fertilization + cattle manure; M, cattle manure; CK, non-fertilization control) on organic carbon (OC) stability, soil iron fractions in bulk soil, and soil aggregates were studied to characterize the capacity and mechanism of Fe minerals to preserve SOM in soil. Long-term fertilization significantly altered the Fe fractions in soil and soil aggregates. The two applications with manure (NPKM and M) increased the non-crystalline Fe content, while the chemical fertilizer (NPK) increased the crystalline Fe content. Besides, long-term fertilization with manure greatly increased the content of SOC and soil total nitrogen (STN). The non-crystalline Fe was positively correlated with the SOC content in both soil and soil aggregates. Meanwhile, the long-term fertilization treatments greatly changed the mass distribution and OC content of soil aggregates. Long-term manure fertilization promoted the formation of non-crystalline Fe fractions, which bounds to SOC to form soil macro-aggregates. Thus, the formation of SOC-Fe association in soil and soil aggregates plays a crucial role in SOC preservation.

Iron-Coupled Anaerobic Oxidation of Methane Performed by a Mixed Bacterial-Archaeal Community Based on Poorly Reactive Minerals.

Anaerobic oxidation of methane (AOM) was shown to reduce methane emissions by over 50% in freshwater systems, its main natural contributor to the atmosphere. In these environments iron oxides can become main agents for AOM, but the underlying mechanism for this process has remained enigmatic. By conducting anoxic slurry incubations with lake sediments amended with 13C-labeled methane and naturally abundant iron oxides the process was evidenced by significant 13C-enrichment of the dissolved inorganic carbon pool and most pronounced when poorly reactive iron minerals such as magnetite and hematite were applied. Methane incorporation into biomass was apparent by strong uptake of 13C into fatty acids indicative of methanotrophic bacteria, associated with increasing copy numbers of the functional methane monooxygenase pmoA gene. Archaea were not directly involved in full methane oxidation, but their crucial participation, likely being mediators in electron transfer, was indicated by specific inhibition of their activity that fully stopped iron-coupled AOM. By contrast, inhibition of sulfur cycling increased 13C-methane turnover, pointing to sulfur species involvement in a competing process. Our findings suggest that the mechanism of iron-coupled AOM is accomplished by a complex microbe-mineral reaction network, being likely representative of many similar but hidden interactions sustaining life under highly reducing low energy conditions.

Impact of Aeolian Dry Deposition of Reactive Iron Minerals on Sulfur Cycling in Sediments of the Gulf of Aqaba.

The Gulf of Aqaba is an oligotrophic marine system with oxygen-rich water column and organic carbon-poor sediments (≤0.6% at sites that are not influenced by anthropogenic impact). Aeolian dust deposition from the Arabian, Sinai, and Sahara Deserts is an important source of sediment, especially at the deep-water sites of the Gulf, which are less affected by sediment transport from the Arava Desert during seasonal flash floods. Microbial sulfate reduction in sediments is inferred from the presence of pyrite (although at relatively low concentrations), the presence of sulfide oxidation intermediates, and by the sulfur isotopic composition of sulfate and solid-phase sulfides. Saharan dust is characterized by high amounts of iron minerals such as hematite and goethite. We demonstrated, that the resulting high sedimentary content of reactive iron(III) (hydr)oxides, originating from this aeolian dry deposition of desert dust, leads to fast re-oxidation of hydrogen sulfide produced during microbial sulfate reduction and limits preservation of reduced sulfur in the form of pyrite. We conclude that at these sites the sedimentary sulfur cycle may be defined as cryptic.

Review of Abiotic Degradation of Chlorinated Solvents by Reactive Iron Minerals in Aquifers

AbstractAbiotic degradation of chlorinated solvents by reactive iron minerals such as iron sulfides, magnetite, green rust, and other Fe(II)‐containing minerals has been observed in both laboratory and field studies. These reactive iron minerals form under iron‐ and sulfate‐reducing conditions which are commonly found in permeable reactive barriers (PRBs), enhanced reductive dechlorination (ERD) treatment locations, landfills, and aquifers that are chemically reducing. The objective of this review is to synthesize current understanding of abiotic degradation of chlorinated solvents by reactive iron minerals, with special focus on how abiotic processes relate to groundwater remediation. Degradation of chlorinated solvents by reactive minerals can proceed through reductive elimination, hydrogenolysis, dehydrohalogenation, and hydrolysis reactions. Degradation products of abiotic reactions depend on degradation pathways and parent compounds. Some degradation products (e.g., acetylene) have the potential to serve as a signature product for demonstrating abiotic reactions. Laboratory and field studies show that various minerals have a range of reactivity toward chlorinated solvents. A general trend of mineral reactivity for degradation of chlorinated solvents can be approximated as follows: disordered FeS &gt; FeS &gt; Fe(0) &gt; FeS2 &gt; sorbed Fe2+ &gt; green rust = magnetite &gt; biotite = vermiculite. Reaction kinetics are also influenced by factors such as pH, natural organic matter (NOM), coexisting metal ions, and sulfide concentration in the system. In practice, abiotic reactions can be engineered to stimulate reactive mineral formation for groundwater remediation. Under appropriate site geochemical conditions, abiotic reactions can occur naturally, and can be incorporated into remedial strategies such as monitored natural attenuation.

Isotopic insights into microbial sulfur cycling in oil reservoirs.

Microbial sulfate reduction in oil reservoirs (biosouring) is often associated with secondary oil production where seawater containing high sulfate concentrations (~28 mM) is injected into a reservoir to maintain pressure and displace oil. The sulfide generated from biosouring can cause corrosion of infrastructure, health exposure risks, and higher production costs. Isotope monitoring is a promising approach for understanding microbial sulfur cycling in reservoirs, enabling early detection of biosouring, and understanding the impact of souring. Microbial sulfate reduction is known to result in large shifts in the sulfur and oxygen isotope compositions of the residual sulfate, which can be distinguished from other processes that may be occurring in oil reservoirs, such as precipitation of sulfate and sulfide minerals. Key to the success of this method is using the appropriate isotopic fractionation factors for the conditions and processes being monitored. For a set of batch incubation experiments using a mixed microbial culture with crude oil as the electron donor, we measured a sulfur fractionation factor for sulfate reduction of −30‰. We have incorporated this result into a simplified 1D reservoir reactive transport model to highlight how isotopes can help discriminate between biotic and abiotic processes affecting sulfate and sulfide concentrations. Modeling results suggest that monitoring sulfate isotopes can provide an early indication of souring for reservoirs with reactive iron minerals that can remove the produced sulfide, especially when sulfate reduction occurs in the mixing zone between formation waters (FW) containing elevated concentrations of volatile fatty acids (VFAs) and injection water (IW) containing elevated sulfate. In addition, we examine the role of reservoir thermal, geochemical, hydrological, operational and microbiological conditions in determining microbial souring dynamics and hence the anticipated isotopic signatures.