Great Oxidation Research Articles

Bacterial growth and environmental adaptation via thiamine biosynthesis and thiamine-mediated metabolic interactions.

Understanding the ancestral transition from anaerobic to aerobic lifestyles is essential for comprehending life's early evolution. However, the biological adaptations occurring during this crucial transition remain largely unexplored. Thiamine is an important cofactor involved in central carbon metabolism and aerobic respiration. Here, we explored the phylogenetic and global distribution of thiamine-auxotrophic and thiamine-prototrophic bacteria based on the thiamine biosynthetic pathway in 154 838 bacterial genomes. We observed strong coincidences of the origin of thiamine-synthetic bacteria with the "Great Oxygenation Event," indicating that thiamine biosynthesis in bacteria emerged as an adaptation to aerobic respiration. Furthermore, we demonstrated that thiamine-mediated metabolic interactions are fundamental factors influencing the assembly and diversity of bacterial communities by a global survey across 4245 soil samples. Through our newly established stable isotope probing-metabolic modeling method, we uncovered the active utilization of thiamine-mediated metabolic interactions by bacterial communities in response to changing environments, thus revealing an environmental adaptation strategy employed by bacteria at the community level. Our study demonstrates the widespread thiamine-mediated metabolic interactions in bacterial communities and their crucial roles in setting the stage for an evolutionary transition from anaerobic to aerobic lifestyles and subsequent environmental adaptation. These findings provide new insights into early bacterial evolution and their subsequent growth and adaptations to environments.

Sedimentary environment and benthic oxygenation history of the Upper Cretaceous Austin Chalk Group, south Texas: An integrated ichnological, sedimentological and geochemical approach

ABSTRACTOxygen concentration in the ocean is vital for sustaining marine ecosystems. While the potential impacts of deoxygenation on modern oceans are hard to predict, lessons can be learned from better characterizing past geological intervals formed under a greenhouse climate. The greenhouse Cretaceous containing several oceanic anoxic events characterized by widespread oxygen‐deficient water is ideal in this regard. The Austin Chalk Group in south Texas (USA) shows organic‐rich intervals that can be linked to oxygen depletion in the ocean, but the exact bottom water oxygenation conditions have not been estimated. This study aims to reconstruct both sediment interstitial and bottom water oxygenation history during Austin Chalk Group deposition by integrating detailed ichnological, sedimentological and geochemical (X‐ray fluorescence and X‐ray diffraction) analyses, thereby providing a consistent model that may be applicable across a range of marine shelf settings. The 141.12 m Gise #1 core contains a continuous record of the Austin Chalk Group, providing an opportunity for unravelling oxygenation and deoxygenation events. Whereas the anaerobic–exaerobic deposits are essentially nonbioturbated, four oxygen‐related ichnocoenoses are defined, further refining the transition of aerobic to dysaerobic conditions in the sediment interstitial water. Omission surfaces and glauconitic grains, products of current‐induced scouring and condensation, suggest sporadic high‐energy events in the Austin Chalk Group ramp that drove elevated terrestrial inputs. Geochemical data further help to identify anoxic bottom water conditions within the anaerobic facies. Additionally, the lowermost part of the Austin Chalk Group illustrates redox cycles, whereas dilution events characterized by elevated terrestrial input are identified throughout the rest of the Austin Chalk Group. The evolution of oxygenation levels in sediment interstitial water and bottom water disputes the existence of a long‐lasting oxygen‐deficient sea in south Texas. The refined depositional model may be applicable to coeval shelfal settings. Moreover, the results provide insights into variable, evolving palaeoclimatic and palaeoceanographic conditions of the greenhouse Late Cretaceous.

Гарганский тип континентальной тектоносферы: Pb-изотопные оценки возраста событий ранней, средней и поздней геодинамических эпох Земли в слоях внешней оболочки, коромантийного перехода и литосферной мантии

From Pb-isotope age estimates of protoliths in sources of Cenozoic volcanic rocks and older dikes and sills, as well as Pb age estimates of galena from ore deposits, we define events of the early, middle, and late geodynamic epochs of the Earth's evolution in the Gargan zone of Eastern Sayans. We connect the tectonosphere development in the early geodynamic epoch with impact events of the Earth in the Hadean and Archean, in the middle one – with the Great Oxidation event in the Early Paleoproterozoic, and in the late one – with tectonic integration of the Gargan zone into the basement of the Tuva-Mongolian microcontinent in the Neoproterozoic and early Paleozoic. The conclusions obtained serve as a basis for identifying the Gargan-type continental tectonosphere.

How Did Thylakoids Emerge in Cyanobacteria, and How Were the Primary Chloroplast and Chromatophore Acquired?

The emergence of thylakoid membranes in cyanobacteria is a key event in the evolution of all oxygenic photosynthetic cells, from prokaryotes to eukaryotes. Recent analyses show that they could originate from a unique lipid phase transition rather than from a supposed vesicular budding mechanism. Emergence of thylakoids coincided with the great oxygenation event, more than two billion years ago. The acquisition of semi-autonomous organelles, such as the mitochondrion, the chloroplast, and, more recently, the chromatophore, is a critical step in the evolution of eukaryotes. They resulted from primary endosymbiotic events that seem to share general features, i.e., an acquisition of a bacterium/cyanobacteria likely via a phagocytic membrane, a genome reduction coinciding with an escape of genes from the organelle to the nucleus, and, finally, the appearance of an active system translocating nuclear-encoded proteins back to the organelles. An intense mobilization of foreign genes of bacterial origin, via horizontal gene transfers, plays a critical role. Some third partners, like Chlamydia, might have facilitated the transition from cyanobacteria to the early chloroplast. This chapter further details our current understanding of primary endosymbiosis, focusing on primary chloroplasts, thought to have appeared over a billion years ago, and the chromatophore, which appeared around a hundred years ago.

Climate variability during the late Ediacaran: Insights from episodic deposition of black shale-hosted Mn‑carbonates in South China

The Ediacaran period witnessed events that were of significance to the evolution of Earth's environment and early life, especially the Neoproterozoic Oxygenation Event during the Shuram Event (ca. 570–562 Ma) that was followed by the rise of animal life. However, the nature of the climate change that followed the Shuram Event in South China remains unclear. Black shale-hosted Mn‑carbonate deposits have the potential to reveal valuable information about paleo-seawater conditions and paleoclimate. This paper presents results of an investigation of the unique Ediacaran mudstone succession of South China, especially black shale-hosted Mn‑carbonate deposits, and offers a new perspective of the interconnected nature of paleoclimate and Ediacaran deposits. Relying on detailed petrological, sedimentological, and geochemical data, we posit that Ediacaran Mn‑carbonates accumulated in a semi-enclosed basin that experienced oscillating water column redox conditions and enhanced primary productivity. Chemical index of alteration (CIA) values, Rb/Sr ratios, and δ13C − δ15N stratigraphy of the analyzed deposits provide evidence of episodic warming during an otherwise protracted cooling trend following the Shuram Event (ca. 562–551 Ma). This study highlights the significant utility of black shale-hosted Mn‑carbonate strata in reconstructing Earth's paleoclimate during transitions.

Reconfiguring oxygenation at ∼1.4 Ga: New constraints as informed by the ancient oceanic sulfur cycle

The extent of atmospheric and oceanic oxygenation during the Mesoproterozoic remains an area of active debate. Here, we report major and trace elements, organic sulfur (OS) speciation, sulfur isotopes in multiple phases [pyrite (py), OS, and carbonate-associated sulfate (CAS)], and a numerical model of sulfate concentrations from one of the Mesoproterozoic's best-preserved geochemical archives, the Xiamaling Formation (ca. 1.4 Ga) in the Yanliao Basin. These data reveal a previously unrecognized ocean-atmosphere oxygenation process. Starting with Unit 3, intense sulfurization increased organic carbon burial and thus oxygen release, resulting in a deep-water oxidation event within the Yanliao Basin that could be regarded as a transient restricted oxygen oasis based on low pyrite content, elevated kerogen S:C ratios, higher δ34Spy than δ34SOS (Δδ34SOS-py < 0), and a low calculated sulfate concentration of ∼0.07–0.14 mM. During Unit 2, the basin was reconnected to the open ocean with the deposition of organic-rich shale across northern China and northern Australia, accompanied by a shift in Δδ34SOS-py to 5.0‰ and a calculated seawater sulfate concentration of ∼0.1–1.14 mM. Such large-scale burial of organic matter released oxygen into the atmosphere, accompanied by significant sulfate delivery to the basin and euxinic conditions characterized by Mo concentrations and 34S-depleted pyrite at the topmost of Unit 2. A subsequent globally synchronized atmospheric and deep ocean oxygenation event may have occurred during Unit 1. This event was recorded by a progressive increase in Δδ34SOS-py (up to +9.6‰), increased oxidized OS species, and positive Ce anomalies (attributed to the reductive dissolution of the Ce-enriched Mn oxides), all of which were caused by increased sulfate concentrations (calculated to be ∼1.15–2.31 mM) and a spatial descent of the redox interface. The combination of these lines of evidence illustrates the sensitivity of the oceanic sulfur cycle to the ocean-atmosphere system and provides novel constraints on oxygenation at ∼1.4 Ga.

Calcitized evaporites in the Mesoproterozoic Atar and El Meriti Groups, Mauritania, Africa

One of the most profound byproducts of the Great Oxidation Event (GOE) was the onset of oxidative weathering on land and the riverine delivery of sulfate to marine systems. Although the exact nature of marine oxygenation in the aftermath of the GOE remains uncertain, marine sulfate likely remained below 2 mM until the late Mesoproterozoic and may have remained <10 mM through the Neoproterozoic. Prior to the late Mesoproterozoic, precipitation of sulfate minerals were inhibited by low marine sulfate and possibly by elevated carbonate saturation. By ∼1.1 Ga marine sulfate concentrations were sufficient to sustain the earliest widespread evaporite deposition. Low sulfate concentrations, however, influenced both the deposition and diagenesis of evaporite deposits. Here we investigate unusual limestone deposits in the 1.1 Ga Atar Group, Mauritania, that contain both macroscopic and microscopic features that suggest a primary origin as gypsum. Elevated concentrations of carbonate-associated sulfate (CAS), sodium, and potassium are consistent with primary deposition as a sulfate evaporite and subsequent calcification under low water-rock ratios. Isotope and elemental compositions further indicate diagenetic recrystallization under marine to hypersaline marine conditions. Combined, these observations show the potential for recognizing key evaporite facies in the rock record and support a growing recognition of late Mesoproterozoic evaporite deposits.

Refining the carbonate-associated iodine redox proxy with leaching experiments

Iodate ions can substitute for carbonate in crystal lattices, which is why carbonate-associated iodine (CAI) is increasingly being used to track redox-sensitive iodine species, and by extrapolation, the redox conditions of ancient oceans. Extracting iodine from carbonate rocks is challenging, however, because iodine is susceptible to volatilization in acidic solutions. A broadly similar leaching scheme with different leaching times has been applied to all kinds of ancient carbonate rocks. However, the effects of non‑carbonate phases and iodine stability during leaching remain under-constrained, which limits its use for paleoredox reconstruction. For this study, we assessed these issues by conducting a series of leaching experiments on carbonate standards and ancient carbonate rocks of varying purity. We first developed an alternative stabilizer for iodine, i.e., 3% EDTA (ethylenediaminetetraacetic acid) in 3% NH4OH (ammonium hydroxide). This easily accessible new stabilizer effectively prevents the precipitation of metal ions from the alkaline solution, thus easing the preparation process and reducing the iodine signal drift during the CAI analysis. We also propose two interlaboratory limestone standards for iodine analysis with long-term (one year) I/Ca values of 0.43 ± 0.03 μmol/mol for limestone CRM-393 and 0.99 ± 0.06 μmol/mol for argillaceous limestone SRM-1c. Here we demonstrate that excessive leaching times (>60 min) can lead to the loss of nearly half of the iodine released under typical leaching conditions. Bulk carbonate digestion is shown to potentially underestimate primary CAI concentrations due to the presence of diagenetic carbonates. Moreover, we identified phosphates and organic matter as potential contaminants, the inadvertent leaching of which could lead to overestimated concentrations. Although the potential significance of such contamination warrants further study, our results show that contamination, if present, can be minimised by oxidative cleaning with 12% NaClO followed by dissolution in 0.3 M acetic acid. The possibility that measured CAI concentrations can be both under- and over-estimated may lead to reassessment of oxygenation events identified from the iodine concentrations of impure carbonate rocks.

A timeline of bacterial and archaeal diversification in the ocean

Microbial plankton play a central role in marine biogeochemical cycles, but the timing in which abundant lineages diversified into ocean environments remains unclear. Here, we reconstructed the timeline in which major clades of bacteria and archaea colonized the ocean using a high-resolution benchmarked phylogenetic tree that allows for simultaneous and direct comparison of the ages of multiple divergent lineages. Our findings show that the diversification of the most prevalent marine clades spans throughout a period of 2.2 Ga, with most clades colonizing the ocean during the last 800 million years. The oldest clades – SAR202, SAR324, Ca. Marinimicrobia, and Marine Group II – diversified around the time of the Great Oxidation Event, during which oxygen concentration increased but remained at microaerophilic levels throughout the Mid-Proterozoic, consistent with the prevalence of some clades within these groups in oxygen minimum zones today. We found the diversification of the prevalent heterotrophic marine clades SAR11, SAR116, SAR92, SAR86, and Roseobacter as well as the Marine Group I to occur near to the Neoproterozoic Oxygenation Event (0.8–0.4 Ga). The diversification of these clades is concomitant with an overall increase of oxygen and nutrients in the ocean at this time, as well as the diversification of eukaryotic algae, consistent with the previous hypothesis that the diversification of heterotrophic bacteria is linked to the emergence of large eukaryotic phytoplankton. The youngest clades correspond to the widespread phototrophic clades Prochlorococcus, Synechococcus, and Crocosphaera, whose diversification happened after the Phanerozoic Oxidation Event (0.45–0.4 Ga), in which oxygen concentrations had already reached their modern levels in the atmosphere and the ocean. Our work clarifies the timing at which abundant lineages of bacteria and archaea colonized the ocean, thereby providing key insights into the evolutionary history of lineages that comprise the majority of prokaryotic biomass in the modern ocean.

A timeline of bacterial and archaeal diversification in the ocean.

Microbial plankton play a central role in marine biogeochemical cycles, but the timing in which abundant lineages diversified into ocean environments remains unclear. Here, we reconstructed the timeline in which major clades of bacteria and archaea colonized the ocean using a high-resolution benchmarked phylogenetic tree that allows for simultaneous and direct comparison of the ages of multiple divergent lineages. Our findings show that the diversification of the most prevalent marine clades spans throughout a period of 2.2 Ga, with most clades colonizing the ocean during the last 800 million years. The oldest clades - SAR202, SAR324, Ca. Marinimicrobia, and Marine Group II - diversified around the time of the Great Oxidation Event, during which oxygen concentration increased but remained at microaerophilic levels throughout the Mid-Proterozoic, consistent with the prevalence of some clades within these groups in oxygen minimum zones today. We found the diversification of the prevalent heterotrophic marine clades SAR11, SAR116, SAR92, SAR86, and Roseobacter as well as the Marine Group I to occur near to the Neoproterozoic Oxygenation Event (0.8-0.4 Ga). The diversification of these clades is concomitant with an overall increase of oxygen and nutrients in the ocean at this time, as well as the diversification of eukaryotic algae, consistent with the previous hypothesis that the diversification of heterotrophic bacteria is linked to the emergence of large eukaryotic phytoplankton. The youngest clades correspond to the widespread phototrophic clades Prochlorococcus, Synechococcus, and Crocosphaera, whose diversification happened after the Phanerozoic Oxidation Event (0.45-0.4 Ga), in which oxygen concentrations had already reached their modern levels in the atmosphere and the ocean. Our work clarifies the timing at which abundant lineages of bacteria and archaea colonized the ocean, thereby providing key insights into the evolutionary history of lineages that comprise the majority of prokaryotic biomass in the modern ocean.

Evidence for high-frequency oxygenation of Ediacaran shelf seafloor during early evolution of complex life

Increasing oxygenation of the early Ediacaran Ocean is thought to have been responsible for the emergence of early animals. Although geochemical studies have suggested periods of oceanic oxygenation in the Ediacaran, direct evidence for seafloor oxygenation has been lacking. Here, we report frequent occurrences of distinctive, sub-millimetric, and early diagenetic pyrite-marcasite rosettes in phosphorites from the lower Ediacaran Doushantuo Formation (Weng’an, South China). They typically consist of a nucleus of framboidal pyrite, a cortex of radiating marcasite blades intergrown with quartz, and a rim of second-generation pyrite, recording partial oxidative dissolution of pyrite and co-precipitation of marcasite and quartz. This inference is further supported by near-zero carbon isotope values of the host dolostone, similarly low sulfur isotope values for pyrite and marcasite, and evident Fe-isotope fractionation between marcasite and pyrite. Collectively, our findings reveal intermittent bottom-water and porewater oxygenation events, providing direct evidence of high-frequency oxygenation of Ediacaran continental shelves.

Outcomes and Direct Cost of Isolated Nonemergent CABG in Patients With Low Ejection Fraction.

Preoperative left ventricular ejection fraction (LVEF) is one of the main predictors of outcomes in cardiac surgery. We present current era outcomes and associated direct cost in nonemergent isolated coronary artery bypass surgery (CABG) patients with LVEF <20% over the past 6 years and compare it with higher EF subgroups. Six-year data from 2016 to 2022 at hospitals sharing Society of Thoracic Surgeons and financial data with Biome Analytics were analyzed based on 3 EF subgroups (EF ≤20%, EF 21% to 35%, and EF >35%). Outcomes and costs were assessed. Overall 30-day mortality of 12,649 patients was 1.9%. The EF ≤20% (n = 248), EF 21% to 35% (n = 1,408), and EF >35 (n = 10,993) cohorts had mortality of 6.9%, 3.7%, and 1.6%, respectively. The EF ≤20% subgroup had higher use of cardiopulmonary bypass, blood products, and mechanical support. In addition, the EF ≤20% subgroup had higher complication rates in almost all measured categories. Also, the EF ≤20% cohort had significantly higher length of stay, intensive care unit (ICU) hours, ICU and hospital readmissions, and lowest discharge to home rate. The strongest factors associated with mortality were postoperative cardiac arrest, renal failure requiring dialysis, extracorporeal membrane oxygenation, sepsis, prolonged ventilation, and gastrointestinal event. The overall median direct cost of care was $37,387.79 ($27,605.18, $51,720.96), with a median direct cost of care in the EF ≤20%, EF 21% to 35%, and EF >35% subgroups of $52,500.17 ($34,103.52, $80,806.79), $44,108.32 ($31,597.58, $63,788.03), and $36,521.80 ($27,168.91, $50,019.31), respectively. In nonemergent isolated CABG surgery, low EF continues to have higher surgical risks and higher direct cost of care despite advances in cardiovascular care.

Impact of aging protocols on asphalt binder behavior: A laboratory and field study

In this study, the focus was on the analysis of asphalt binder aging, a complex process that induces physical, chemical, and rheological changes in these materials, affecting the performance of asphalt mixtures over time. While thermal-oxidative aging is well-documented, the aspects of photo-oxidative aging and the influence of moisture are frequently overlooked. The investigation assessed 50/70 asphalt binder that underwent short-term and long-term aging in both laboratory and field climatic conditions in Brazil. Initially, these binders underwent short-term aging using the Rolling Thin-Film Oven (RTFO) method. Subsequently, the binders were subjected to prolonged aging, exposing them to heat, oxygen, UV radiation, and moisture. The chemical results unveiled distinct reaction mechanisms during thermal and photochemical aging processes. Greater oxidation was observed when binders were exposed to UV radiation, while the oven protocol resulted in increased binder stiffness. Following prolonged aging, a noticeable increase in binder stiffness was observed, particularly when exposed to a temperature of 85 °C. Concurrently, a decrease in fatigue resistance at high strains and a reduction in permanent deformations were identified after aging. The effects of UV radiation were less pronounced than anticipated, mainly due to the lower chamber temperature (60 °C). Nevertheless, the applied stimuli expedited the aging process, underscoring the significance of including UV radiation and moisture in laboratory aging studies. Additionally, it was observed that the aging protocol at 85 °C yielded results analogous to those observed under field conditions over a six-month period in the northeastern region of Brazil.

Rare earth element and yttrium (REY) geochemistry of 3.46–2.45 Ga greenalite-bearing banded iron formations: New insights into iron deposition and ancient ocean chemistry

Finely laminated cherts enclosing nanoparticles of greenalite and apatite are ubiquitous in Archean-Paleoproterozoic (3.46–2.45 Ga) ferruginous cherts, jaspilites and Banded Iron Formations (BIFs) and the greenalite and apatite are considered to be primary deposits. The cherts and BIFs are chemical sedimentary rocks interpreted to have been precipitated in marine settings prior to the first permanent rise in atmospheric oxygen at the Great Oxidation Event (GOE) ca. 2.45–2.32 M.y. ago. As chemical sediments, they are potential archives of the solutions from which they precipitated, incorporating signals from hydrothermal fluids and ambient seawater. Previous studies of rare earth elements and Y (REY) in pre-GOE BIFs have mostly found an “Archean seawater signature” with positive Eu anomalies, attributed to the influence of high-temperature hydrothermal processes, and positive anomalies for La, Gd and Y, ascribed to seawater. REY abundances determined by in situ LA-ICP-MS are presented for well-preserved, laminated greenalite-bearing cherts from ten formations of pre-GOE ferruginous cherts and BIFs from Western Australia. The samples come from a wide range of depositional environments, e.g., submarine proximal volcanic environments, basin floor, slope and deep marine shelf, and are between 3.46 Ga to 2.45 Ga in age. Five groups with different REY patterns are identified, namely (i) mafic-volcanic-influenced vent-proximal chert from the Marble Bar Chert Member of the Duffer Formation of the Warrawoona Group; (ii) felsic volcanic- and sediment-associated chert from the Kangaroo Caves Formation of the Sulphur Springs Group and the Wilgie Mia Formation of the Murchison Supergroup, (iii) ferruginous cherts in shelf sediments from the Bee Gorge Member of the Wittenoom Formation of the Hamersley Group, (iv) BIFs from the Nammuldi Member of the Marra Mamba Iron Formation and Joffre Member of the Brockman Iron Formation, Hamersley Group, and (v) BIFs from the Dales Gorge Member of the Brockman Iron Formation. Of these, only the Dales Gorge Member BIF has a typical Archean seawater signature while the others have REY patterns likely reflecting differing source fluids and environments of deposition but not necessarily global ocean chemistry. Analyses of chert containing sub-micron-sized particles of greenalite and apatite indicate that the likely hosts of the REEs are apatite, siderite and possibly greenalite. The REY patterns of the greenalite-bearing cherts may differ from those of bulk samples of the same formations, perhaps reflecting a diagenetic overprint in the bulk samples, whereas the greenalite-bearing cherts likely preserve their depositional compositions, locked in by early silicification.

Natural ocean iron fertilization and climate variability over geological periods.

Marine primary producers are largely dependent on and shape the Earth's climate, although their relationship with climate varies over space and time. The growth of phytoplankton and associated marine primary productivity in most of the modern global ocean is limited by the supply of nutrients, including the micronutrient iron. The addition of iron via episodic and frequent events drives the biological carbon pump and promotes the sequestration of atmospheric carbon dioxide (CO2 ) into the ocean. However, the dependence between iron and marine primary producers adaptively changes over different geological periods due to the variation in global climate and environment. In this review, we examined the role and importance of iron in modulating marine primary production during some specific geological periods, that is, the Great Oxidation Event (GOE) during the Huronian glaciation, the Snowball Earth Event during the Cryogenian, the glacial-interglacial cycles during the Pleistocene, and the period from the last glacial maximum to the late Holocene. Only the change trend of iron bioavailability and climate in the glacial-interglacial cycles is consistent with the Iron Hypothesis. During the GOE and the Snowball Earth periods, although the bioavailability of iron in the ocean and the climate changed dramatically, the changing trend of many factors contradicted the Iron Hypothesis. By detangling the relationship among marine primary productivity, iron availability and oceanic environments in different geological periods, this review can offer some new insights for evaluating the impact of ocean iron fertilization on removing CO2 from the atmosphere and regulating the climate.

Genomic Approaches and Analyses of Slow-Growing Obligate Iron-Metabolizing Microbes

The biogeochemical cycling of iron is a vastly important process that has been a major factor defining life on Earth both before and after the Great Oxidation Event. While both abiotic and biotic factors contributing to the iron cycle have been studied for many years, the bulk of studies on iron metabolizing organisms has focused on a select few, easily manipulated model organisms. Recent discoveries have identified several unique and difficult to work with organisms from iron rich environments that survive solely on iron as either an electron acceptor or donor. The Fe(III)-reducing, Gram-positive Firmicute Metallumcola ferriviriculae MK1 was recently isolated from the Soudan Underground Mine in northern Minnesota from brine waters that intersect 2.7 Ga banded iron formations within the Canadian Shield. M. ferriviriculae MK1, which grows anaerobically using Fe(III)-citrate as its sole electron acceptor, is also mesophilic, spore-forming, culturable, and rich in multiheme cytochromes. Multiheme cytochromes are a well-established mechanism for Fe(III) reduction among the model Gram-negative microbes, such as Shewanella oneidensis and Geobacter sulfurreducens, but is poorly studied in Gram-positives. While the slow growth times of M. ferriviriculae MK1 make it difficult to study in the laboratory, the genome encodes homologs to multiheme cytochromes utilized by G. sulfurreducens for Fe(III) reduction. Specifically, two gene clusters (MK1_2258-2259 and MK1_2264-2265) each encode proteins homologous to the b-type cytochrome domain (60% and 61% sequence similarity, respectively) and c-type cytochrome domain (44.9% and 47.14%, respectively) of cbcL, which is used for reduction of mid-range redox potential acceptors in G. sulfurreducens and MK1_1670 is homologous to imcH (54.3% sequence similarity), which is used for higher redox potential acceptors. Additionally, the MK1 genome contains genes associated with sporulation, including genes encoding the master sporulation regulator spo0A, the peptidoglycan remodeling enzymes spoIID, spoIIP, and spoIIM, the spore morphogenesis protein spoIVA, and the small, acid-soluble spore proteins sspA, sspB, sspC, sspD, and sspF. Extraction and isolation of MK1 spores will facilitate evaluation of sporulation and germination conditions to shed light on a crucial preservation mechanism from an organism found in an environment with limited nutrients. Further evaluation into this novel organism can also give us insights into the microbial impacts on the iron cycle in the deep terrestrial biosphere. Another microbe of interest that was isolated from an iron-rich environment is the obligate Fe(II)-oxidizing Mariprofundus ferrooxydans PV-1, which was enriched from iron-rich mats associated with hydrothermal vents at the Kama’ehuakanaloa Seamount (previously Lo’ihi) in Hawaii. M. ferrooxydans PV-1 is a stalk-forming Fe(II)-oxidizing microbe and the first Zetaproteobacterium characterized. While M. ferrooxydans PV-1 can reliably be grown (doubling time of ~12 hours) in liquid medium traditional genetic methods are challenging because it does not make colonies on agar plates. To identify essential and non-essential genes, we developed a conjugation method using E. coli and successfully generated a transposon library in M. ferrooxydans. Libraries were grown under kanamycin selection with Fe(II)-chloride as the sole electron donor and samples isolated for analysis at two different timepoints. Deep sequencing of the mutant population at these timepoints was performed and the reads were mapped back to the M. ferrooxydans PV-1 genome to identify transposon insertion sites. Initial evaluation of the reads has identified 31 transposon insertion sites found within both the first- and second-generation populations, with 21 hits representing stable insertions in non-essential genes, including a predicted malate dehydrogenase (SPV1_772) and a predicted phospholipase (SPV1_8286), that may be useful future targets for gene insertion sites. Further evaluation comparing the read depth between the generations should identify genes that were selected for or against during the subculturing. These studies and approaches are providing insights into the roles these challenging, non-model organisms are performing in iron-rich environments, which provides a better context for the biogeochemical cycling of iron in relevant biospheres.

Using a novel approach to characterize the surface reactivities of silica-rich ferrihydrite and biogenic cyanobacteria-ferrihydrite aggregates and the implications for Archean ocean geochemistry

Precambrian banded iron formations (BIF) are iron- and silica-rich chemical sedimentary rocks that are commonly used as paleo-redox proxies for Archean and Paleoproterozoic seawater geochemistry. At the onset of the Great Oxidation Event (herein GOE) around 2.4 Ga, cyanobacteria flourished with increasing nutrient fluxes due to oxidative weathering on land. In turn, this led to increased primary productivity that facilitated the permanent shift from a reducing Earth atmosphere to an oxidizing one. Interestingly, the duration of GOE also overlapped with one of the most prolific periods of BIF deposition.It is widely accepted that cyanobacteria were likely responsible for BIF formation during the GOE. Oxidation of dissolved Fe(II) by oxygen produced from cyanobacteria forms a metastable and amorphous mineral phase ferrihydrite, Fe(OH)3. As an essential component in both ancient BIF deposits and various modern ecosystems, the surface reactivity of ferrihydrite has been extensively studied under different conditions (i.e., pH and ionic strengths). Not only are the highly reactive surfaces of ferrihydrite particles important shuttles for trace element transport from the water column to the sediment pile, but previous studies have also demonstrated that cyanobacterial cells and ferrihydrite tend to aggregate at seawater pH. This means that ferrihydrite was also a vector for the transport of organic carbon to the seafloor. However, a complicating issue is how co-ions affect the surface reactivity of ferrihydrite, specifically dissolved silica which was abundant in ancient seawater. Although previous studies have demonstrated that silica can passivate the surface reactivity of ferrihydrite, what remains unclear is how silica impacts ferrihydrite-biomass aggregation. To fill this knowledge gap, we formed both silica-spiked ferrihydrite and cyanobacteria-ferrihydrite aggregates in situ and subsequently conducted empirical potentiometric acid-base titrations and Cd adsorption experiments on the fresh aggregate samples at three different ionic strengths (0.56 M, 0.1 M and 0.01 M). We minimized sample processing (i.e., drying and powdering) to a simple washing step, in which the aggregate pellets remained hydrated to avoid any mineral transformation thus altering their true surface reactivity in seawater. Experimental results were then fitted with non-electrostatic model to predict both surface charges and metal-adsorption behavior of ferrihydrite aggregates. Different from previous surface-complexation modelling studies, here we used a novel and more powerful modelling program called Phreefit. It utilizes the global optimization algorithms instead of more commonly used Newton-Raphson method in FITEQL program, which is often too limited for precisely modelling complex systems such as the two samples in this study. Furthermore, we also measured the surface charges of both samples over the pH range from 3 to 9 on a Malvern Zetasizer and characterized the surface functional groups through Fourier-Transform Infrared Spectroscopy to help with our interpretation of the experimental data.Preliminary results show that cyanobacteria-ferrihydrite aggregates formed primarily due to ionic bridging. Cyanobacterial cells likely facilitated the precipitation of dissolved silica. Findings from titration and Cd adsorption experiments indicate that the surface reactivity and capacity of both silica-rich ferrihydrite cyanobacteria-ferrihydrite aggregates to adsorb trace elements differ from their individual components, likely due to site blockage. This distinction is particularly prominent when considering the expected Archean seawater pH from 6 to 8. This disparity implies that the biogenic ferrihydrite aggregates do not exhibit an additive surface reactivity, which is in agreement with similar previous studies. Our combined results are crucial to accurately predict the adsorption of trace elements onto the aggregate surface and, ultimately, comprehend the archive of trace elements in sedimentary rocks used to reconstruct Precambrian ocean chemistry.

Hydrocarbon generation potential and organic matter accumulation patterns in organic-rich shale during the mesoproterozoic oxygenation event: evidence from the Xiamaling formation shale

A significant deposition of black shales occurred during the Mesoproterozoic Oxygenation Event (MOE). In order to investigate the hydrocarbon generation potential and organic matter enrichment mechanism of these shale deposits, we studied the Xiamaling Formation shale in the North China region as a representative sample of the Mesoproterozoic shale. The research involved organic petrology, organic geochemistry, mineralogy, and elemental geochemistry. The following observations were made: (1) The depositional environment of the Xiamaling Formation shale can be categorized as either oxic or anoxic, with the former having shallow depositional waters and high deposition rates, while the latter has deeper depositional waters and slower deposition rates. (2) Anoxic shales exhibited significantly better hydrocarbon generation potential compared to shales deposited in oxic environments, although the latter still demonstrated high hydrocarbon generation potential. (3) Shales deposited in anoxic environments displayed higher paleoproductivity compared to those deposited in oxic environments. The high deposition rate in oxic environments slowed the decomposition and mineralization of organic matter, leading to the formation of high-quality shales. In contrast, the strong paleoproductivity, along with favorable preservation conditions, accounted for the high hydrocarbon potential of anoxic shales.

Hg isotope evidence for oceanic oxygenation during the Cambrian Explosion

The Cambrian explosion is a critical evolutionary milestone in life history, but the mechanistic relationship between the Cambrian explosion, rising atmospheric and oceanic oxygen levels, and the primary productivity remains controversial. Here, we present new mercury (Hg) isotope data from Cambrian marine sediments of the ∼521–514 Ma Yu’anshan and Shuijingtuo Formations (Nanhua Basin, South China), which preserve the famous ∼518 Ma Chengjiang and Qingjiang Cambrian Biotas, respectively. We find evidence that, prior to Cambrian animal diversification, local terrestrial and/or atmospheric inputs are important drivers of Hg enrichment in the shallow shelf Yu’anshan and Shuijintuo Formations. Elevated Hg and total organic carbon (TOC) concentrations of coeval deeper shelf and slope sections of the Niutitang Formation are mainly attributed to upwelling of Hg associated with dissolved organic carbon (Hg-DOC) from pelagic seawater, unrelated to locally high primary productivity. During the deposition of fossiliferous strata, negative shifts of Δ199Hg and δ202Hg values in the shallow water shelf shales from the Shuijingtuo Formation, combined with similar Hg isotope characteristics in the deeper shelf and slope shales, demonstrate a significant shallow and deep-water oxygenation event took place in the Nanhua Basin. A comparable negative shift of Δ199Hg values occurs in coeval Indian Craton sediments, suggesting this oxygenation event could be regional, or possibly even global, in scale. Our newly-collected Hg isotope data provide strong evidence that rising molecular oxygen levels in both surface and deep seawater are associated with enhanced marine primary productivity and could be a critical driver of the Cambrian explosion. Finally, we also argue that Hg isotopes are an emerging and promising redox proxy for studies of Precambrian seawater, but the chemical response of Hg to atmospheric and ocean oxygenation requires further calibration.

The geologic history of primary productivity

The rate of primary productivity is a keystone variable in driving biogeochemical cycles today and has been throughout Earth's past.1 For example, it plays a critical role in determining nutrient stoichiometry in the oceans,2 the amount of global biomass,3 and the composition of Earth's atmosphere.4 Modern estimates suggest that terrestrial and marine realms contribute near-equal amounts to global gross primary productivity (GPP).5 However, this productivity balance has shifted significantly in both recent times6 and through deep time.7,8 Combining the marine and terrestrial components, modern GPP fixes≈250 billion tonnes of carbon per year (Gt C year-1).5,9,10,11 A grand challenge in the study of the history of life on Earth has been to constrain the trajectory that connects present-day productivity to the origin of life. Here, we address this gap by piecing together estimates of primary productivity from the origin of life to the present day. We estimate that ∼1011-1012 Gt C has cumulatively been fixed through GPP (≈100 times greater than Earth's entire carbon stock). We further estimate that 1039-1040 cells have occupied the Earth to date, that more autotrophs than heterotrophs have ever existed, and that cyanobacteria likely account for a larger proportion than any other group in terms of the number of cells. We discuss implications for evolutionary trajectories and highlight the early Proterozoic, which encompasses the Great Oxidation Event (GOE), as the time where most uncertainty exists regarding the quantitative census presented here.