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USGS2011

Future directions in geobiology and low-temperature geochemistry

Humanity is confronted with an enormous challenge, as succinctly stated by the late Steven Schneider (2001; quoted by Jantzen 2004*): “Humans are forcing the Earth’s environmental systems to change at a rate that is more advanced than their knowledge of the consequences.” Geobiologists and low-temperature geochemists characterize material from the lithosphere, hydrosphere, atmosphere, and biosphere to understand processes operating within and between these components of the Earth system from the atomic to the planetary scale. For this reason, the interwoven disciplines of geobiology and low-temperature geochemistry are central to understanding and ultimately predicting the behavior of these life-sustaining systems. We present here comments and recommendations from the participants of a workshop entitled “Future Directions in Geobiology and Low-Temperature Geochemistry,” hosted by the Carnegie Institution of Washington, Geophysical Laboratory, Washington, DC, on 27–28 August 2010. The goal of the workshop was to suggest ways to leverage the vast intellectual and analytical capabilities of our diverse scientific community to characterize the Earth’s past, present, and future geochemical habitat as we enter the second decade of what E. O. Wilson dubbed “the century of the environment.”

Elements↗

USGS2014

The geobiology of sediment-hosted mineral deposits

The role of biological processes in the formation of sediment-hosted ore deposits has long been recognized. In this review, we focus on the biogeochemical cycling of C, Mn, Fe, and S as they relate to the formation of sediment-hosted Mn and Fe deposits, metalliferous black shales, clastic-dominated (CD) Pb-Zn deposits, and phosphorites. Biological mediation of ore-forming processes occurs over large spans of space and time. The most important step is oxygenic photosynthesis, a biological innovation dating from the Archean Eon that releases free oxygen into the surface oceans and atmosphere and delivers chemical potential, in the form of reduced carbon, to the seafloor. Photosynthetic oxygen is available to precipitate dissolved Fe 2 + and Mn 2 +, and therefore it augments the formation of sedimentary Mn and Fe deposits, and drives oxidative weathering of exposed crust, thereby delivering sulfate and transition metals to the ocean. Where reduced carbon accumulates in the deep oceans and on the seafloor, bacterial sulfate reduction produces hydrogen sulfide thereby facilitating the formation of metalliferous black shales, sediment-hosted Pb and Zn sulfide deposits, and phosphorites. Thus, an understanding of major biogeochemical processes and how they have evolved over time is required in order to refine genetic models for sediment-hosted ore deposits and to guide future mineral exploration. A close secular relationship between deposit formation and trends in major biogeochemical cycles provides a potentially powerful tool for mineral resource assessment. Sedimentary basins that formed during a time that is known to lack deposits of a particular metal can be eliminated during exploration programs, whereas others of permissive ages should be considered priorities. For example, sedimentary basins older than ca. 1.8 Ga are unlikely to contain large CD Pb-Zn deposits, and basins that formed between 1.6 and 0.6 Ga are not prospective for phosphorites. Recent technological advances in the application of nanometer-, micron-, and bulk-scale analytical techniques allow for imaging of complex biological structures and have provided new insights into the role of bacteria, not only in direct formation of mineral deposits, but also in leaching of metals from ore and mineralized rocks. Future exploration for, and exploitation of, mineral deposits may include offshore or land-based, low-grade, high-tonnage targets; understanding the role of bacteria in mineral growth, mineral dissolution, and redox transformations will aid in predicting where such deposits exist, and how metal extraction from ores can be enhanced.

Book chapter↗

USGS2024

The early Earth as an analogue for exoplanetary biogeochemistry

Planet Earth has evolved over the past 4.5 billion years from an entirely anoxic planet with possibly a different tectonic regime to the oxygenated world with horizontal plate tectonics that we know today. For most of this time, Earth has been inhabited by a purely microbial biosphere albeit with seemingly increasing complexity over time. A rich record of this geobiological evolution over most of Earth’s history thus provides insights into the remote detectability of microbial life under a variety of planetary conditions. Here we leverage Earth’s geobiological record with the aim of (a) illustrating the current state of knowledge and key knowledge gaps about the early Earth as a reference point in exoplanet science research; (b) compiling biotic and abiotic mechanisms that controlled the evolution of the atmosphere over time; and (c) reviewing current constraints on the detectability of Earth’s early biosphere with state-of-the-art telescope technology. We highlight that life may have originated on a planet with a different (stagnant lid) tectonic regime and strong hydrothermal activity, and under these conditions, biogenic CH 4 gas was perhaps the most detectable atmospheric biosignature. Oxygenic photosynthesis, which is responsible for essentially all O 2 gas in the modern atmosphere, appears to have emerged concurrently with the establishment of modern plate tectonics and the emergence of continental crust, but O 2 accumulation to modern levels only occurred late in Earth’s history, perhaps tied to the rise of land plants. Nutrient limitation in anoxic oceans, promoted by hydrothermal Fe fluxes, may have limited biological productivity and O 2 production. N 2 O is an alternative biosignature that was perhaps significant on the redox-stratified Proterozoic Earth. We conclude that the detectability of atmospheric biosignatures on Earth was not only dependent on biological evolution but also strongly controlled by the evolving tectonic context.

Reviews in Mineralogy and Geochemistry↗

USGS2021

The Sedimentary Geochemistry and Paleoenvironments Project

Geobiology explores how Earth's system has changed over the course of geologic history and how living organisms on this planet are impacted by or are indeed causing these changes. For decades, geologists, paleontologists, and geochemists have generated data to investigate these topics. Foundational efforts in sedimentary geochemistry utilized spreadsheets for data storage and analysis, suitable for several thousand samples, but not practical or scalable for larger, more complex datasets. As results have accumulated, researchers have increasingly gravitated toward larger compilations and statistical tools. New data frameworks have become necessary to handle larger sample sets and encourage more sophisticated or even standardized statistical analyses.

Geobiology↗

USGS2026

Structural evolution of iron coordination in proteins across Earth’s oxygenation history

Protein metal-binding sites support essential biological functions shaped by protein fold, subunit interactions, and cofactor chemistry. Because these sites encode both biochemical function and environmental constraint, they offer a route to connect protein evolution with changes in Earth’s surface environment through time. Of particular interest is iron (Fe), the most widely used metal in biology and a cofactor central to both anaerobic and aerobic metabolism. Here, we systematically compare the immediate chemical environments of functionally essential Fe-binding sites in three-dimensional protein structures to test whether Fe coordination spheres differ across oxygen contexts. Using a curated dataset of experimentally determined structures, we identify a clear shift in the local chemistry of Fe-binding environments from anaerobic to aerobic proteins. Aerobic Fe sites are significantly more hydrophilic than anaerobic ones, and amino-acid composition analyses show reduced cysteine use in aerobic Fe-binding neighborhoods. These patterns suggest that as Earth’s surface environments became more oxygenated, proteins retained Fe as a core redox metal while reconfiguring local coordination chemistry in ways less vulnerable to oxidative damage. More broadly, this study introduces and applies the Coordination Sphere Analysis and Comparison (CSAC) workflow, an open and archived Python workflow for extracting local metal-binding environments from structure datasets, providing a framework for linking metalloprotein structure to evolutionary and geobiological transitions across Earth history.

Discover Life↗

USGS2017

Expanding the role of reactive transport models in critical zone processes

Models test our understanding of processes and can reach beyond the spatial and temporal scales of measurements. Multi-component Reactive Transport Models (RTMs), initially developed more than three decades ago, have been used extensively to explore the interactions of geothermal, hydrologic, geochemical, and geobiological processes in subsurface systems. Driven by extensive data sets now available from intensive measurement efforts, there is a pressing need to couple RTMs with other community models to explore non-linear interactions among the atmosphere, hydrosphere, biosphere, and geosphere. Here we briefly review the history of RTM development, summarize the current state of RTM approaches, and identify new research directions, opportunities, and infrastructure needs to broaden the use of RTMs. In particular, we envision the expanded use of RTMs in advancing process understanding in the Critical Zone, the veneer of the Earth that extends from the top of vegetation to the bottom of groundwater. We argue that, although parsimonious models are essential at larger scales, process-based models offer tools to explore the highly nonlinear coupling that characterizes natural systems. We present seven testable hypotheses that emphasize the unique capabilities of process-based RTMs for (1) elucidating chemical weathering and its physical and biogeochemical drivers; (2) understanding the interactions among roots, micro-organisms, carbon, water, and minerals in the rhizosphere; (3) assessing the effects of heterogeneity across spatial and temporal scales; and (4) integrating the vast quantity of novel data, including “omics” data (genomics, transcriptomics, proteomics, metabolomics), elemental concentration and speciation data, and isotope data into our understanding of complex earth surface systems. With strong support from data-driven sciences, we are now in an exciting era where integration of RTM framework into other community models will facilitate process understanding across disciplines and across scales.

Earth-Science Reviews↗

USGS2023

The dynamic influence of subsurface geological processes on the assembly and diversification of thermophilic microbial communities in continental hydrothermal systems

An accepted paradigm of hydrothermal systems is the process of phase separation, or boiling, of a deep, homogeneous hydrothermal fluid as it ascends through the subsurface resulting in gas rich and gas poor fluids. While phase separation helps to explain first-order patterns in the chemistry and biology of a hot spring’s surficial expression, we know little about the subsurface architecture beneath “phase-separated” pools and the timescales over which phase separation processes occur. Essentially, we have a two-dimensional understanding of a four-dimensional process. By combining geophysical, geochemical, isotopic, and microbiological measurements of two adjacent phase-separated hot springs in Norris Geyser Basin, Yellowstone National Park, we provide a four-dimensional assessment of phase separation processes and their biological manifestation. We uniquely show that Yellowstone’s hydrothermal waters originate from a deep sedimentary aquifer and that both meteoric recharge and shallow reactive transport processes are required to establish the geobiological feedbacks that drive bimodal distributions in the geochemical and microbial composition of hot springs. Specifically, over periods of tens of years, gas-enriched fluids containing volcanic sulfide mix with meteoric waters resulting in microbially-mediated production of sulfuric acid by thermoacidophilic Archaea in the near subsurface. In contrast, over periods of hundreds of years, anoxic residual liquid rises to the surface where it is infused with atmospheric gas fostering Archaea and Bacteria that are largely dependent on oxygen. As such, our results provide formative insight into the causative links between subsurface geological processes, the development of geochemical fluids, and the assembly and diversification of thermophilic microbial communities in hydrothermal systems.

Wyoming↗

USGS2020

Trends in thermal maturity indicators for the organic sulfur-rich Eagle Ford Shale

Thermal maturity is critical to evaluate petroleum systems and to interpret biomarker results for paleoenvironmental and geobiology studies. Many thermal maturity indices were developed for marine source rocks containing type II kerogen, but their behavior in organic sulfur-rich source rocks requires more investigation. Here, we present geochemical analyses of whole and extracted rock, isolated kerogens, and extractable organic matter across a natural thermal maturity transect of the Upper Cretaceous Eagle Ford Shale to evaluate the behavior of maturity parameters in organic sulfur-rich source rocks. The samples contain similar mineralogy and trace element composition, minimizing potential facies effects on thermal maturity parameters. Atomic H/C ratios of isolated kerogens, extractable organic matter yield, and programmed pyrolysis results show that the samples range from the pre-oil through dry gas generation windows. Programmed pyrolysis data and kerogen elemental ratios show that the immature samples host both type IIS (atomic Sorg/C > 0.04) and sulfur-rich type II kerogen (kerogen Sorg/C: 0.032 to 0.045) while the samples with lower kerogen Sorg/C ratios (kerogen Sorg/C < 0.03) are more mature. The vitrinite reflectance values corresponding to the onset of oil generation in the Eagle Ford are comparable to other type II petroleum systems. Likewise, the organic sulfur-rich Eagle Ford follows a similar hydrogen index and kerogen H/C trend as other marine type II source rocks. Hopane and sterane stereoisomer maturity ratios are anomalously elevated at low thermal maturities, so they should not be applied in organic sulfur-rich petroleum systems to infer thermal maturity. However, some biomarker ratios, including those that are more commonly used as source parameters, strongly track thermal maturity in this case study with limited facies variability.

Texas↗

USGS2013

Challenge theme 5: Current and future needs of energy and mineral resources in the Borderlands and the effects of their development: Chapter 7 in United States-Mexican Borderlands: Facing tomorrow's challenges through USGS science

Exploration and extraction activities related to energy and mineral resources in the Borderlands—such as coal-fired power plants, offshore drilling, and mining—can create issues that have potentially major economic and environmental implications. Resource assessments and development projects, environmental studies, and other related evaluations help to understand some of these issues, such as power plant emissions and the erosion/denudation of abandoned mine lands. Information from predictive modeling, monitoring, and environmental assessments are necessary to understand the full effects of energy and mineral exploration, development, and utilization. The exploitation of these resources can negatively affect human health and the environment, its natural resources, and its ecological services (air, water, soil, recreation, wildlife, etc.). This chapter describes the major energy and mineral issues of the Borderlands and how geologic frameworks, integrated interdisciplinary (geobiologic) investigations, and other related studies can address the anticipated increases in demands on natural resources in the region.

United States-Mexico Borderlands↗

USGS2015

Dominance of 'Gallionella capsiferriformans' and heavy metal association with Gallionella -like stalks in metal-rich pH 6 mine water discharge

Heavy metal-contaminated, pH 6 mine water discharge created new streams and iron-rich terraces at a creek bank in a former uranium-mining area near Ronneburg, Germany. The transition from microoxic groundwater with ~5 m m Fe(II) to oxic surface water may provide a suitable habitat for microaerobic iron-oxidizing bacteria (FeOB). In this study, we investigated the potential contribution of these FeOB to iron oxidation and metal retention in this high-metal environment. We (i) identified and quantified FeOB in water and sediment at the outflow, terraces, and creek, (ii) studied the composition of biogenic iron oxides ( Gallionella -like twisted stalks) with scanning and transmission electron microscopy (SEM, TEM) as well as confocal laser scanning microscopy (CLSM), and (iii) examined the metal distribution in sediments. Using quantitative PCR, a very high abundance of FeOB was demonstrated at all sites over a 6-month study period. Gallionella spp. clearly dominated the communities, accounting for up to 88% of Bacteria , with a minor contribution of other FeOB such as Sideroxydans spp. and ‘ Ferrovum myxofaciens ’. Classical 16S rRNA gene cloning showed that 96% of the Gallionella -related sequences had ≥97% identity to the putatively metal-tolerant ‘ Gallionella capsiferriformans ES-2’, in addition to known stalk formers such as Gallionella ferruginea and Gallionellaceae strain R-1. Twisted stalks from glass slides incubated in water and sediment were composed of the Fe(III) oxyhydroxide ferrihydrite, as well as polysaccharides. SEM and scanning TEM-energy-dispersive X-ray spectroscopy revealed that stalk material contained Cu and Sn, demonstrating the association of heavy metals with biogenic iron oxides and the potential for metal retention by these stalks. Sequential extraction of sediments suggested that Cu (52–61% of total sediment Cu) and other heavy metals were primarily bound to the iron oxide fractions. These results show the importance of ‘ G. capsiferriformans ’ and biogenic iron oxides in slightly acidic but highly metal-contaminated freshwater environments.

Geobiology↗

USGS2017

Volcanic ash supports a diverse bacterial community in a marine mesocosm

Shallow-water coral reef ecosystems, particularly those already impaired by anthropogenic pressures, may be highly sensitive to disturbances from natural catastrophic events, such as volcanic eruptions. Explosive volcanic eruptions expel large quantities of silicate ash particles into the atmosphere, which can disperse across millions of square kilometres and deposit into coral reef ecosystems. Following heavy ash deposition, mass mortality of reef biota is expected, but little is known about the recovery of post-burial reef ecosystems. Reef regeneration depends partly upon the capacity of the ash deposit to be colonised by waterborne bacterial communities and may be influenced to an unknown extent by the physiochemical properties of the ash substrate itself. To determine the potential for volcanic ash to support pioneer bacterial colonisation, we exposed five well-characterised volcanic and coral reef substrates to a marine aquarium under low light conditions for 3 months: volcanic ash, synthetic volcanic glass, carbonate reef sand, calcite sand and quartz sand. Multivariate statistical analysis of Automated Ribosomal Intergenic Spacer Analysis (ARISA) fingerprinting data demonstrates clear segregation of volcanic substrates from the quartz and coral reef substrates over 3 months of bacterial colonisation. Overall bacterial diversity showed shared and substrate-specific bacterial communities; however, the volcanic ash substrate supported the most diverse bacterial community. These data suggest a significant influence of substrate properties (composition, granulometry and colour) on bacterial settlement. Our findings provide first insights into physicochemical controls on pioneer bacterial colonisation of volcanic ash and highlight the potential for volcanic ash deposits to support bacterial diversity in the aftermath of reef burial, on timescales that could permit cascading effects on larval settlement.

Geobiology↗

USGS2019

The importance of groundwater flow to the formation of modern thrombolitic microbialites

Modern microbialites are often located within groundwater discharge zones, yet the role of groundwater in microbialite accretion has yet to be resolved. To understand relationships between groundwater, microbialites, and associated microbial communities, we quantified and characterized groundwater flow and chemistry in active thrombolitic microbialites in Lake Clifton, Western Australia, and compared these observations to inactive thrombolites and lakebed sediments. Groundwater flows upward through an interconnected network of pores within the microstructure of active thrombolites, discharging directly from thrombolite heads into the lake. This upwelling groundwater is fresher than lake water and is hypothesized to support microbial mat growth by reducing salinity and providing limiting nutrients in an osmotically stressful and oligotrophic habitat. This is in contrast to inactive thrombolites that show no evidence of microbial mat colonization and are infiltrated by hypersaline lake water. Groundwater discharge through active thrombolites contrasts with the surrounding lakebed, where hypersaline lake water flows downward through sandy sediments at very low rates. Based on an appreciation for the role of microorganisms in thrombolite accretion, our findings suggest conditions favorable to thrombolite formation still exist in certain locations of Lake Clifton despite increasing lake water salinity. This study is the first to characterize groundwater flow rates, paths, and chemistry within a microbialite‐forming environment and provides new insight into how groundwater can support microbial mats believed to contribute to microbialite formation in modern and ancient environments.

Geobiology↗

USGS2021

New geochemical tools for investigating resource and energy functions at deep-sea cold seeps using amino-acid δ15N in chemosymbiotic mussels (Bathymodiolus childressi)

In order to reconstruct the ecosystem structure of chemosynthetic environments in the fossil record, geochemical proxies must be developed. Here, we present a suite of novel compound-specific isotope parameters for tracing chemosynthetic production with a focus on understanding nitrogen dynamics in deep-sea cold seep environments. We examined the chemosymbiotic bivalve Bathymodiolus childressi from three geographically distinct seep sites on the NE Atlantic Margin and compared isotope data to non-chemosynthetic littoral mussels to test whether water depth, seep activity, and/or mussel bed size are linked to differences in chemosynthetic production. The bulk isotope analysis of carbon (δ 13 C) and nitrogen (δ 15 N), and δ 15 N values of individual amino acids (δ 15 N AA ) in both gill and muscle tissues, as well as δ 15 N AA- derived parameters including trophic level (TL), baseline δ 15 N value (δ 15 N Phe ), and a microbial resynthesis index (Σ V ), were used to investigate specific geochemical signatures of chemosynthesis. Our results show that δ 15 N AA values provide a number of new proxies for relative reliance on chemosynthesis, including TL, ∑V, and both δ 15 N values and molar percentages (Gly/Glu mol% index) of specific AA. Together, these parameters suggested that relative chemoautotrophy is linked to both degree of venting from seeps and mussel bed size. Finally, we tested a Bayesian mixing model using diagnostic AA δ 15 N values, showing that percent contribution of chemoautotrophic versus heterotrophic production to seep mussel nutrition can be directly estimated from δ 15 N AA values. Our results demonstrate that δ 15 N AA analysis can provide a new set of geochemical tools to better understand mixotrophic ecosystem function and energetics, and suggest extension to the study of ancient chemosynthetic environments in the fossil record.

Geobiology↗

USGS2021

Potential role for microbial ureolysis in the rapid formation of carbonate tufa mounds

Modern carbonate tufa towers in the alkaline (~pH 9.5) Big Soda Lake (BSL), Nevada, exhibit rapid precipitation rates (exceeding 3 cm/year) and host diverse microbial communities. Geochemical indicators reveal that carbonate precipitation is, in part, promoted by the mixing of calcium-rich groundwater and carbonate-rich lake water, such that a microbial role for carbonate precipitation is unknown. Here, we characterize the BSL microbial communities and evaluate their potential effects on carbonate precipitation that may influence fast carbonate precipitation rates of the active tufa mounds of BSL. Small subunit rRNA gene surveys indicate a diverse microbial community living endolithically, in interior voids, and on tufa surfaces. Metagenomic DNA sequencing shows that genes associated with metabolisms that are capable of increasing carbonate saturation (e.g., photosynthesis, ureolysis, and bicarbonate transport) are abundant. Enzyme activity assays revealed that urease and carbonic anhydrase, two microbial enzymes that promote carbonate precipitation, are active in situ in BSL tufa biofilms, and urease also increased calcium carbonate precipitation rates in laboratory incubation analyses. We propose that, although BSL tufas form partially as a result of water mixing, tufa-inhabiting microbiota promote rapid carbonate authigenesis via ureolysis, and potentially via bicarbonate dehydration and CO 2 outgassing by carbonic anhydrase. Microbially induced calcium carbonate precipitation in BSL tufas may generate signatures preserved in the carbonate microfabric, such as stromatolitic layers, which could serve as models for developing potential biosignatures on Earth and elsewhere.

Geobiology↗

USGS2024

Deep-water first occurrences of Ediacara biota prior to the Shuram carbon isotope excursion in the Wernecke Mountains, Yukon, Canada

Ediacara-type macrofossils appear as early as ~575 Ma in deep-water facies of the Drook Formation of the Avalon Peninsula, Newfoundland, and the Nadaleen Formation of Yukon and Northwest Territories, Canada. Our ability to assess whether a deep-water origination of the Ediacara biota is a genuine reflection of evolutionary succession, an artifact of an incomplete stratigraphic record, or a bathymetrically controlled biotope is limited by a lack of geochronological constraints and detailed shelf-to-slope transects of Ediacaran continental margins. The Ediacaran Rackla Group of the Wernecke Mountains, NW Canada, represents an ideal shelf-to-slope depositional system to understand the spatiotemporal and environmental context of Ediacara-type organisms' stratigraphic occurrence. New sedimentological and paleontological data presented herein from the Wernecke Mountains establish a stratigraphic framework relating shelfal strata in the Goz/Corn Creek area to lower slope deposits in the Nadaleen River area. We report new discoveries of numerous Aspidella hold-fast discs, indicative of frondose Ediacara organisms, from deep-water slope deposits of the Nadaleen Formation stratigraphically below the Shuram carbon isotope excursion (CIE) in the Nadaleen River area. Such fossils are notably absent in coeval shallow-water strata in the Goz/Corn Creek region despite appropriate facies for potential preservation. The presence of pre-Shuram CIE Ediacara-type fossils occurring only in deep-water facies within a basin that has equivalent well-preserved shallow-water facies provides the first stratigraphic paleobiological support for a deep-water origination of the Ediacara biota. In contrast, new occurrences of Ediacara-type fossils (including juvenile fronds, Beltanelliformis , Aspidella , annulated tubes, and multiple ichnotaxa) are found above the Shuram CIE in both deep- and shallow-water deposits of the Blueflower Formation. Given existing age constraints on the Shuram CIE, it appears that Ediacaran organisms may have originated in the deeper ocean and lived there for up to ~15 million years before migrating into shelfal environments in the terminal Ediacaran. This indicates unique ecophysiological constraints likely shaped the initial habitat preference and later environmental expansion of the Ediacara biota.

Geobiology↗

USGS2010

Microbial production of isotopically light iron(II) in a modern chemically precipitated sediment and implications for isotopic variations in ancient rocks

The inventories and Fe isotope composition of aqueous Fe(II) and solid-phase Fe compounds were quantified in neutral-pH, chemically precipitated sediments downstream of the Iron Mountain acid mine drainage site in northern California, USA. The sediments contain high concentrations of amorphous Fe(III) oxyhydroxides [Fe(III) am ] that allow dissimilatory iron reduction (DIR) to predominate over Fe–S interactions in Fe redox transformation, as indicated by the very low abundance of Cr(II)-extractable reduced inorganic sulfur compared with dilute HCl-extractable Fe. δ 56 Fe values for bulk HCl- and HF-extractable Fe were ≈ 0. These near-zero bulk δ 56 Fe values, together with the very low abundance of dissolved Fe in the overlying water column, suggest that the pyrite Fe source had near-zero δ 56 Fe values, and that complete oxidation of Fe(II) took place prior to deposition of the Fe(III) oxide-rich sediment. Sediment core analyses and incubation experiments demonstrated the production of millimolar quantities of isotopically light (δ 56 Fe ≈ -1.5 to -0.5) aqueous Fe(II) coupled to partial reduction of Fe(III) am by DIR. Trends in the Fe isotope composition of solid-associated Fe(II) and residual Fe(III) am are consistent with experiments with synthetic Fe(III) oxides, and collectively suggest an equilibrium Fe isotope fractionation between aqueous Fe(II) and Fe(III) am of approximately -2. These Fe(III) oxide-rich sediments provide a model for early diagenetic processes that are likely to have taken place in Archean and Paleoproterozoic marine sediments that served as precursors for banded iron formations. Our results suggest pathways whereby DIR could have led to the formation of large quantities of low-δ 56 Fe minerals during BIF genesis.

California↗

USGS2011

Microbial reduction of structural iron in interstratified illite-smectite minerals by a sulfate-reducing bacterium

Clay minerals are ubiquitous in soils, sediments, and sedimentary rocks and could coexist with sulfate‐reducing bacteria (SRB) in anoxic environments, however, the interactions of clay minerals and SRB are not well understood. The objective of this study was to understand the reduction rate and capacity of structural Fe(III) in dioctahedral clay minerals by a mesophilic SRB, Desulfovibrio vulgaris and the potential role in catalyzing smectite illitization. Bioreduction experiments were performed in batch systems, where four different clay minerals (nontronite NAu‐2, mixed‐layer illite‐smectite RAr‐1 and ISCz‐1, and illite IMt‐1) were exposed to D. vulgaris in a non‐growth medium with and without anthraquinone‐2,6‐disulfonate (AQDS) and sulfate. Our results demonstrated that D. vulgaris was able to reduce structural Fe(III) in these clay minerals, and AQDS enhanced the reduction rate and extent. In the presence of AQDS, sulfate had little effect on Fe(III) bioreduction. In the absence of AQDS, sulfate increased the reduction rate and capacity, suggesting that sulfide produced during sulfate reduction reacted with the phyllosilicate Fe(III). The extent of bioreduction of structural Fe(III) in the clay minerals was positively correlated with the percentage of smectite and mineral surface area of these minerals. X‐ray diffraction, and scanning and transmission electron microscopy results confirmed formation of illite after bioreduction. These data collectively showed that D. vulgaris could promote smectite illitization through reduction of structural Fe(III) in clay minerals.

Geobiology↗