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The exploration of Mars has revealed that its ancient surface hosted lakes with a dazzling array of chemical and physical conditions and processes. The potential habitability of surface waters has driven studies aimed at understanding whether or not Mars once hosted life. High levels of atmospheric carbon dioxide are probable on early Mars, which means that lakes derived from weathering fluids could have contained substantial carbonate alkalinity. Recent studies show that lakes with high carbonate alkalinity are able to concentrate the phosphate and cyanide that are critical for molecular synthesis in the origin of life. While evidence for carbonate-rich Martian lakes remains limited, NASA’s Perseverance rover may reveal clues about the past existence of such waters in Jezero Crater.

To interpret microbially influenced paleoenvironments in the sedimentary record, it is crucial to understand what processes control the development of microbial mats in modern environments. This article reports results from a multiyear study of Little Ambergris Cay, Turks and Caicos Islands, an uninhabited island floored by broad tracts of well-developed microbial mats on the wind-dominated and wave-dominated Caicos Platform. Uncrewed aerial vehicle-based imaging, differential global positioning system topographic surveys, radiocarbon data, and in situ sedimentological and microbial ecological observations were integrated to identify and quantify the environmental factors that influence the distribution and morphologies of Little Ambergris Cay microbial mats, including their response to large storm events. Based on these data, this study proposes that Little Ambergris Cay initially developed from the accretion and rapid lithification of carbonate sediment delivered by converging wave fronts in the lee of adjacent Big Ambergris Cay. Broad tracts of microbial mats developed during late Holocene time as the interior became restricted due to beach ridge development. Minor elevation differences regulate subaerial exposure time and lead to three categories of microbial mats, differentiated by surface texture and morphology: smooth mats, polygonal mats and blister mats. The surface texture and morphology of the mats is controlled by subaerial exposure time. In addition to elevation, the spatial distribution of mats is largely controlled by hydrodynamics and sediment transport during large storm events. This detailed assessment of the controls on mat formation and preservation at Little Ambergris Cay provides a framework within which to identify and understand the interactions between microbial communities and sediment transport processes in ancient high-energy carbonate depositional systems.

The history of Earth’s carbon cycle reflects trends in atmospheric composition convolved with the evolution of photosynthesis. Fortunately, key parts of the carbon cycle have been recorded in the carbon isotope ratios of sedimentary rocks. The dominant model used to interpret this record as a proxy for ancient atmospheric CO 2 is based on carbon isotope fractionations of modern photoautotrophs, and longstanding questions remain about how their evolution might have impacted the record. Therefore, we measured both biomass (ε p ) and enzymatic (ε Rubisco ) carbon isotope fractionations of a cyanobacterial strain ( Synechococcus elongatus PCC 7942) solely expressing a putative ancestral Form 1B rubisco dating to ≫1 Ga. This strain, nicknamed ANC, grows in ambient pCO 2 and displays larger ε p values than WT, despite having a much smaller ε Rubisco (17.23 ± 0.61‰ vs. 25.18 ± 0.31‰, respectively). Surprisingly, ANC ε p exceeded ANC ε Rubisco in all conditions tested, contradicting prevailing models of cyanobacterial carbon isotope fractionation. Such models can be rectified by introducing additional isotopic fractionation associated with powered inorganic carbon uptake mechanisms present in Cyanobacteria, but this amendment hinders the ability to accurately estimate historical pCO 2 from geological data. Understanding the evolution of rubisco and the CO 2 concentrating mechanism is therefore critical for interpreting the carbon isotope record, and fluctuations in the record may reflect the evolving efficiency of carbon fixing metabolisms in addition to changes in atmospheric CO 2 .

Sedimentological, textural, and microscale analyses of the Mount McRae Shale revealed a complex postdepositional history, previously unrecognized in bulk geochemical studies. We found that metal enrichments in the shale do not reside with depositional organic carbon, as previously proposed by Anbar et al ., but with late-stage pyrite, compromising claims for a “whiff” of oxygen ~50 million years before the Great Oxygenation Event.

Form I rubiscos evolved in Cyanobacteria ≥2.5 billion years ago and are enzymatically unique due to the presence of small subunits (RbcS) that cap both ends of an octameric large subunit (RbcL) rubisco assembly to form a hexadecameric (L8S8) holoenzyme. Although RbcS was previously thought to be integral to Form I rubisco stability, the recent discovery of a closely related sister clade of octameric rubiscos (Form I’; L8) demonstrates that the enzyme complex assembles without small subunits (Banda et al. 2020). Rubisco also displays a kinetic isotope effect (KIE) where the 3PG product is depleted in13C relative to12C. In Cyanobacteria only two Form I KIE measurements exist, making interpretation of bacterial carbon isotope data difficult. To aid comparison, we measuredin vitrothe KIEs of Form I’ (CandidatusPromineofilum breve) and Form I (Synechococcus elongatusPCC 6301) rubiscos and found the KIE to be smaller in the L8rubisco (16.25 ± 1.36‰ vs. 22.42 ± 2.37‰ respectively). Therefore, while small subunits may not be necessary for protein stability, they may affect the KIE. Our findings may provide insight into the function of RbcS and allow more refined interpretation of environmental carbon isotope data.

Phosphorus (P) availability exerts a strong influence on primary productivity in global oceans. However, its abundance and role as a limiting nutrient prior to the start of the Great Oxygenation Event (GOE) 2.45–2.32 Ga is unclear. Low concentrations of seawater P have been proposed to explain the apparent delay between the early appearance of oxygen-producing Cyanobacteria and the onset of atmospheric oxygenation. We report evidence for seawater precipitation of Ca-phosphate nanoparticles in 2.46–2.40 Ga iron formations deposited on a marine shelf, including shallow-water facies, immediately prior to the onset of the GOE. Our modeling shows that the co-precipitation of Ca-phosphate and ferrous silicate (greenalite) required ferruginous seawater with dissolved P concentrations many orders of magnitude higher than in today’s photic zone. If correct, it follows that P availability is unlikely to have suppressed the expansion of Cyanobacteria prior to the GOE. A reservoir of P-rich surface water shortly before 2.40 Ga could ultimately have triggered a rapid rise in atmospheric oxygen by fueling a sharp increase in primary productivity and organic-carbon burial. We speculate that the enigmatic Lomagundi positive carbon-isotope excursion, recorded in 2.32–2.06 Ga shallow-water carbonates, may mark a key step in the transition toward a modern biosphere of high biological productivity controlled by nutrient availability.

Cyanobacteria rely on CO 2 -concentrating mechanisms (CCMs) to grow in today’s atmosphere (0.04% CO 2 ). These complex physiological adaptations require ≈15 genes to produce two types of protein complexes: inorganic carbon (Ci) transporters and 100+ nm carboxysome compartments that encapsulate rubisco with a carbonic anhydrase (CA) enzyme. Mutations disrupting any of these genes prohibit growth in ambient air. If any plausible ancestral form—i.e., lacking a single gene—cannot grow, how did the CCM evolve? Here, we test the hypothesis that evolution of the bacterial CCM was “catalyzed” by historically high CO 2 levels that decreased over geologic time. Using an E. coli reconstitution of a bacterial CCM, we constructed strains lacking one or more CCM components and evaluated their growth across CO 2 concentrations. We expected these experiments to demonstrate the importance of the carboxysome. Instead, we found that partial CCMs expressing CA or Ci uptake genes grew better than controls in intermediate CO 2 levels (≈1%) and observed similar phenotypes in two autotrophic bacteria, Halothiobacillus neapolitanus and Cupriavidus necator . To understand how CA and Ci uptake improve growth, we model autotrophy as colimited by CO 2 and HCO 3 − , as both are required to produce biomass. Our experiments and model delineated a viable trajectory for CCM evolution where decreasing atmospheric CO 2 induces an HCO 3 − deficiency that is alleviated by acquisition of CA or Ci uptake, thereby enabling the emergence of a modern CCM. This work underscores the importance of considering physiology and environmental context when studying the evolution of biological complexity.

The modern Pacific Ocean hosts the largest oxygen-deficient zones (ODZs), where oxygen concentrations are so low that nitrate is used to respire organic matter. The history of the ODZs may offer key insights into ocean deoxygenation under future global warming. In a 12-My record from the southeastern Pacific, we observe a >10‰ increase in foraminifera-bound nitrogen isotopes (15N/14N) since the late Miocene (8 to 9 Mya), indicating large ODZs expansion. Coinciding with this change, we find a major increase in the nutrient content of the ocean, reconstructed from phosphorus and iron measurements of hydrothermal sediments at the same site. Whereas global warming studies cast seawater oxygen concentrations as mainly dependent on climate and ocean circulation, our findings indicate that modern ODZs are underpinned by historically high concentrations of seawater phosphate., Proceedings of the National Academy of Sciences of the United States of America, 119 (45), ISSN:0027-8424, ISSN:1091-6490

The 1.88-billion-year-old Gunflint carbonaceous microfossils are renowned for their exceptional morphological and chemical preservation, attributed to early and rapid entombment in amorphous silica. The carbonaceous matter lining and partly filling filamentous and spherical structures is interpreted to be indigenous, representing thermally altered relicts of cellular material (i.e., kerogen). Here we show that stromatolitic black cherts from the Gunflint Formation, Schreiber Beach, Ontario, Canada, were saturated in syn-sedimentary oil. The thermally altered oil (pyrobitumen), which occurs in the stromatolites and intercolumn sediments, fills pores and fractures, and coats detrital and diagenetic grain surfaces. The occurrence of detrital bitumen grains in the stromatolites points to the proximity of shallow seafloor oil seeps and hence the possible existence of chemosynthetic microbes degrading hydrocarbons. We suggest that hydrocarbons that migrated through the silicifying stromatolites infiltrated semi-hollow microbial molds that formed following silica nucleation on the walls or sheaths of decayed cells. Upon heating, the hydrocarbons were transformed to nanoporous pyrobitumen, retarding silica recrystallization and enhancing detailed preservation of the carbon-rich microfossils. Hydrocarbon infiltration of silicified microbes offers a new explanation for the preservation of the Gunflint microfossils and may have played a role in the formation of some of Earth's oldest microfossils.

The history of Earth’s carbon cycle reflects trends in atmospheric composition convolved with the evolution of photosynthesis. Fortunately, key parts of the carbon cycle have been recorded in the carbon isotope ratios of sedimentary rocks. The dominant model used to interpret this record as a proxy for ancient atmospheric CO2is based on carbon isotope fractionations of modern photoautotrophs, and longstanding questions remain about how their evolution might have impacted the record. We tested the intersection of environment and evolution by measuring both biomass (εp) and enzymatic (εRubisco) carbon isotope fractionations of a cyanobacterial strain (Synechococcus elongatusPCC 7942) solely expressing a putative ancestral Form 1B rubisco dating to ≫1 Ga. This strain, nicknamed ANC, grows in ambient pCO2and displays larger εpvalues than WT, despite having a much smaller εRubisco(17.23 ± 0.61‰ vs. 25.18 ± 0.31‰ respectively). Measuring both enzymatic and biomass fractionation revealed a surprising result—ANC εpexceeded ANC εRubiscoin all conditions tested, contradicting prevailing models of cyanobacterial carbon isotope fractionation. However, these models were corrected by accounting for cyanobacterial physiology, notably the CO2concentrating mechanism (CCM). Our model suggested that additional fractionating processes like powered inorganic carbon uptake systems contribute to εp, and this effect is exacerbated in ANC. Understanding the evolution of rubisco and the CCM is therefore critical for interpreting the carbon isotope record. Large fluctuations in that record may reflect the evolving efficiency of carbon fixing metabolisms in addition to changes in atmospheric CO2.Significance StatementEarth scientists rely on chemical fossils like the carbon isotope record to derive ancient atmospheric CO2concentrations, but interpretation of this record is calibrated using modern organisms. We tested this assumption by measuring the carbon isotope fractionation of a reconstructed ancestral rubisco enzyme (>1 billion years old)in vivoandin vitro. Our results contradicted prevailing models of carbon flow in Cyanobacteria, but our data could be rationalized if light-driven uptake of CO2is taken into account. Our study showed that the carbon isotope record tracks both the evolution of photosynthesis physiology as well as changes in atmospheric CO2, highlighting the value of considering both evolution and physiology for comparative biological approaches to understanding Earth’s history.

Cyanobacteria rely on CO2 concentrating mechanisms (CCMs) that depend on ≈15 genes to produce two protein complexes: an inorganic carbon (Ci) transporter and a 100+ nm carboxysome compartment that encapsulates rubisco with a carbonic anhydrase (CA) enzyme. Mutations disrupting CCM components prohibit growth in today’s atmosphere (0.04% CO2), indicating that CCMs evolved to cope with declining environmental CO2. Indeed, geochemical data and models indicate that atmospheric CO2 has been generally decreasing from high concentrations over the last ≈3.5 billion years. We used a synthetic reconstitution of a bacterial CCM in E. coli to study the co-evolution of CCMs with atmospheric CO2. We constructed strains expressing putative ancestors of modern CCMs — strains lacking one or more CCM components — and evaluated their growth in a variety of CO2 concentrations. Partial forms expressing CA or Ci uptake genes grew better than controls in intermediate CO2 levels (≈1%); we observed similar phenotypes in genetic studies of two autotrophic bacteria, H. neapolitanus and C. necator. To explain how partial CCMs improve growth, we advance a model of co-limitation of autotrophic growth by CO2 and HCO3-, as both are required to produce biomass. Our model and results delineated a viable trajectory for bacterial CCM evolution where decreasing atmospheric CO2 induces an HCO3- deficiency that is alleviated by acquisition of CAs or Ci uptake genes, thereby enabling the emergence of a modern CCM. This work underscores the importance of considering physiology and environmental context when studying the evolution of biological complexity.SignificanceThe greenhouse gas content of the ancient atmosphere is estimated using models and measurements of geochemical proxies. Some inferred high ancient CO2 levels using models of biological CO2 fixation to interpret the C isotopes found in preserved organic matter. Others argued that elevated CO2 could reconcile a faint young Sun with evidence for liquid water on Earth. We took a complementary “synthetic biological” approach to understanding the composition of the ancient atmosphere by studying present-day bacteria engineered to resemble ancient autotrophs. By showing that it is simpler to rationalize the emergence of modern bacterial autotrophs if CO2 was once high, these investigations provided independent evidence for the view that CO2 concentrations were significantly elevated in the atmosphere of early Earth.

The Phanerozoic Eon marked a major transition from marine silica deposition exclusively via abiotic pathways to a system dominated by biogenic silica sedimentation. For decades, prevailing ideas predicted this abiotic-to-biogenic transition were marked by a significant decrease in the concentration of dissolved silica in seawater; however, due to the lower perceived abundance and uptake affinity of sponges and radiolarians relative to diatoms, marine dissolved silica is thought to have remained elevated above modern values until the Cenozoic radiation of diatoms. Studies of modern marine silica biomineralizers demonstrated that the Si isotope ratios (δ30 Si) of sponge spicules and planktonic silica biominerals produced by diatoms or radiolarians can be applied as quantitative proxies for past seawater dissolved silica concentrations due to differences in Si isotope fractionations among these organisms. We undertook 446 ion microprobe analyses of δ30 Si and δ18 O of sponge spicules and radiolarians from Ordovician-Silurian chert deposits of the Mount Hare Formation in Yukon, Canada. These isotopic data showed that sponges living in marine slope and basinal environments displayed small Si isotope fractionations relative to coeval radiolarians. By constructing a mathematical model of the major fluxes and reservoirs in the marine silica cycle and the physiology of silica biomineralization, we found that the concentration of dissolved silica in seawater was less than ~150 μM during early Paleozoic time-a value that is significantly lower than previous estimates. We posit that the topology of the early Paleozoic marine silica cycle resembled that of modern oceans much more closely than previously assumed.

Phosphorus is an essential nutrient that is thought to have regulated primary productivity in global oceans after the advent of oxygenic photosynthesis. The prime source of seawater phosphorus is regarded to be continental weathering of phosphate minerals. Ancient seawater phosphorus concentrations have been constrained using the phosphorus content of iron-rich chemical sediments—banded iron formations (BIFs); however, the removal processes and depositional phases remain unclear. Here we report that nanometer-sized apatite crystals (

What matters for mudrocks Rock such as slate and shale, which form from mud, suddenly start appearing in the geologic record around 450 million years ago. Their appearance at about the same time as certain plants seems to implicate plant roots in the formation of these ubiquitous rocks. Zeichner et al. found a different route for creating the flocculation required for mudrock. Using analog experiments, the authors found that organic matter from plants alone was sufficient for the formation of flocs—aggregates of small silt and clay particles—which are required to deposit mudrock. This observation could explain the appearance of these rocks in places where the plants did not have deep roots. Science , this issue p. 526

The Ediacaran age (ca. 570 Ma) Shuram excursion, a ca. 12‰ depletion in δ¹³C_(carb), may record a dramatic oxidation of marine sediments associated with a reorganization of Earth’s carbon cycle closely preceding the rise of large metazoans. However, several geochemical indicators suggest it may instead record secondary processes affecting the sediments such as post-depositional alteration. The stable isotopic composition of iron incorporated within carbonates (δ⁵⁶Fe_(carb)) reveals an anomalous ⁵⁶Fe-depletion (down to -1.05‰) in strata containing the Shuram excursion, while the underlying and overlying strata have crustal ⁵⁶Fe-δ⁵⁶Fe_(carb) values. These depleted δ⁵⁶Fe_(carb) data during the Shuram excursion reflect incomplete reduction of iron oxides, limited by low ambient organic carbon contents. This elevated pulse of sedimentary iron oxides would consume the majority of the limited pool of organic carbon and therefore would give rise to very low net organic carbon burial during a time of enhanced detrital delivery of oxidized iron to the sediments. These results imply a syndepositional origin for the Shuram excursion, which represents a shift in the redox composition of Earth’s sedimentary shell toward more oxidizing conditions, perhaps removing a long-lived buffer on atmospheric oxygen.

Sedimentary basins are the archives of ancient environmental conditions on planetary surfaces, and on Mars they may contain the best record of surface water and habitable conditions. While erosional valley networks have been mapped, the global distribution of fluvial sedimentary deposits on Mars has been unknown. Here we generated an eight-trillion-pixel global map of Mars using data from the NASA Context Camera (CTX), aboard the Mars Reconnaissance Orbiter spacecraft, to perform the first systematic global survey of fluvial ridges—exhumed ancient deposits that have the planform shape of river channels or channel belts, but stand in positive relief due to preferential erosion of neighboring terrain. We used large fluvial ridges (>70 m width) as a conservative proxy for the occurrence of depositional rivers or river-influenced depositional areas. Results showed that fluvial ridges are as much as 100 km long, common across the southern highlands, occur primarily in networks within intercrater plains, and are not confined to impact basins. Ridges were dominantly found in Noachian through Late Hesperian units, consistent with cessation of valley network activity, and occurred downstream from valley networks, indicating regional source-to-sink transport systems. These depositional areas mark a globally distributed class of sedimentary deposits that contain a rich archive of Mars history, including fluvial activity on early Mars.

Biogeochemical cycling of sulfur is relatively understudied in terrestrial environments compared to marine environments. However, the comparative ease of access, observation, and sampling of terrestrial settings can expand our understanding of organisms and processes important in the modern sulfur cycle. Furthermore, these sites may allow for the discovery of useful process analogs for ancient sulfur-metabolizing microbial communities at times in Earth's past when atmospheric O2 concentrations were lower and sulfide was more prevalent in Earth surface environments. We identified a new site at Santa Paula Creek (SPC) in Ventura County, CA—a remarkable freshwater, gravel-bedded mountain stream charged with a range of oxidized and reduced sulfur species and heavy hydrocarbons from the emergence of subsurface fluids within the underlying sulfur- and organic-rich Miocene-age Monterey Formation. SPC hosts a suite of morphologically distinct microbial biofacies that form in association with the naturally occurring hydrocarbon seeps and sulfur springs. We characterized the geology, stream geochemistry, and microbial facies and diversity of the Santa Paula Creek ecosystem. Using geochemical analyses and 16S rRNA gene sequencing, we found that SPC supports a dynamic sulfur cycle that is largely driven by sulfide-oxidizing microbial taxa, with contributions from smaller populations of sulfate-reducing and sulfur-disproportionating taxa. This preliminary characterization of SPC revealed an intriguing site in which to study geological and geochemical controls on microbial community composition and to expand our understanding of sulfur cycling in terrestrial environments.

Among the earliest consequences of climate change are extreme weather and rising sea levels—two challenges to which coastal environments are particularly vulnerable. Often found in coastal settings are microbial mats—complex, stratified microbial ecosystems that drive massive nutrient fluxes through biogeochemical cycles and have been important constituents of Earth’s biosphere for eons. Little Ambergris Cay, in the Turks and Caicos Islands, supports extensive mats that vary sharply with relative water level. We characterized the microbial communities across this variation to understand better the emerging threat of sea level rise. In September 2017, the eyewall of category 5 Hurricane Irma transited the island. We monitored the impact and recovery from this devastating storm event. New mat growth proceeded rapidly, with patterns suggesting that storm perturbation may facilitate the adaptation of these ecosystems to changing sea level. Sulfur cycling, however, displayed hysteresis, stalling for >10 months after the hurricane and likely altering carbon storage potential.

The transport and deposition of mud in rivers are key processes in fluvial geomorphology and biogeochemical cycles. Recent work indicates that flocculation might regulate fluvial mud transport by increasing mud settling velocities, but we lack a calibrated mechanistic model for flocculation in freshwater rivers. Here, we developed and calibrated a semi-empirical model for floc diameter and settling velocity in rivers. We compiled a global data set of river suspended sediment concentration-depth profiles and inverted them for in situ settling velocity using the Rouse-Vanoni equation. On average, clay and silt (diameters

Anomalous sulfur isotope compositions present in Archean rocks have been intensely scrutinized over the last 20 years because they record key aspects of Earth's atmospheric composition prior to the appearance of free molecular oxygen ca. 2.3 billion years ago. These isotopic compositions can be described as mass anomalous fractionations (MAF) and are produced in the atmosphere as UV light interacts with SO2 molecules. Most interpretations suggest that atmospheric processes generate a reduced S-phase with a positive (33S-enriched) MAF signature, as measured in pyrites, and an oxidized S-phase with a negative anomaly, as measured in bedded barite deposits. However, recent data for carbonate-associated sulfate (CAS) — a direct proxy for the isotopic composition of sulfur from seawater sulfate — in Neoarchean rocks showed no such negative values, but rather the opposite. To understand if the positive MAF anomalies we measured in Neoarchean CAS reflect secondary processes (diagenetic, metamorphic, handling) instead of original signals of Archean seawater sulfate, we collected additional sample suites with various degrees of preservation and metamorphic alteration across the Campbellrand-Malmani platform in South Africa. Results illustrate that within this comprehensive suite, less-altered samples all contain positive MAF values while secondary processes tend to either remove CAS from the sample and/or decrease the 33S-enrichment. This positive MAF signal in sulfate is therefore reasonably interpreted as a primary depositional origin, and implies that the assumption that sulfate always carries a negative MAF anomaly throughout the Archean rock record needs to be reconsidered. Our CAS observations suggest that future experiments and calculations should also consider atmospheric and/or sulfur cycling processes that can produce oxidized sulfur with a positive MAF signature.

The cycle of organic carbon through the atmosphere, oceans, continents and mantle reservoirs is a hallmark of Earth. Over geological time, chemical exchanges between those reservoirs have produced a diversity of reduced carbon materials that differ in their molecular structures and reactivity. This reactive complexity challenges the canonical dichotomy between the surface and deep, short-term and long-term organic carbon cycle. Old and refractory carbon materials are not confined to the lithosphere but are ubiquitous in the surface environment, and the lithosphere hosts various forms of reduced carbon that can be very reactive. The biological and geological pathways that drive the organic carbon cycle have changed through time; from a synthesis of these changes, it emerges that although a biosphere is required to produce organic carbon, mortality is required to ensure its export to the lithosphere, and graphitization is essential for its long-term stabilization in the solid Earth. Among the by-products of the organic carbon cycle are the accumulation of a massive lithospheric reservoir of organic carbon, the accumulation of dioxygen in the atmosphere and the rise of a terrestrial biosphere. Besides driving surface weathering reactions, free dioxygen has allowed the evolution of new metabolic pathways to produce and respire organic carbon. From the evolution of photosynthesis until the expansion of biomineralization in the Phanerozoic, inorganic controls on the organic carbon cycle have diversified, tightening the connection between the biosphere and geosphere. A review of the organic carbon cycle explores the interactions between the Earth’s surface and deeper reservoirs, the expanding inorganic controls on the organic carbon cycle, and how these links have strengthened through geological time.

Fluid flow in the upper crust not only impacts the redistribution of heat and elements, driving the formation of economic ore deposits, but it also exerts control on metamorphism, metasomatism, and deformation. However, reconstructing the history of fluid flow in ancient basins is exceedingly difficult, particularly in Archean sedimentary rocks because of extensive overprinting and recrystallization. Here, we report U-Pb ages for monazite and xenotime that grew in bedding-parallel veins in 2.63–2.5-b.y.-old shales along the southern Pilbara craton, Australia. The U-Pb ages define six discrete populations, at 2.41 Ga, 2.30 Ga, 2.20 Ga, 2.10 Ga, 2.05 Ga, and 1.66 Ga, which formed ≥200 m.y. after deposition. The abundance of bedding-parallel crack-seal and fibrous veins in banded iron formations (BIFs) and underlying shales suggests a history of episodic buildup of fluid pressure followed by microfracturing, fluid expulsion, and mineral growth. Thermometry of vein minerals indicates temperatures between 230 °C and 320 °C, implicating the migration of hydrothermal fluids. The development of bedding-parallel veins at 2.41 Ga, 2.20 Ga, and 1.66 Ga was coeval with regional orogenic events known to have affected the craton, whereas vein growth at 2.30 Ga, 2.10 Ga, and 2.05 Ga reveals new episodes of deformation and fluid flow. Our results show that well-preserved Archean shales devoid of structural fabrics and >150 km inboard of the craton margin preserve a cryptic history of fluid overpressure, crack-seal vein development, and hydrothermal fluid flow between 2.41 and 1.66 b.y. ago.

The redox state of Earth's surface is controlled on geological timescales by the flow of electrons through the sedimentary rock cycle, mediated largely by the weathering and burial of C‐S‐Fe phases. These processes buffer atmospheric pO₂. At the same time, CO₂ influxes and carbonate burial control seawater acid‐base chemistry and climate over long timescales via the carbonate‐silicate cycle. However, these two systems are mechanistically linked and impact each other via charge balance in the hydrosphere. Here, we use a low‐order Earth system model to interrogate a subset of these connections, with a focus on changes that occur during perturbations to electron flow through the sedimentary rock cycle. We show that the net oxidation or reduction of the Earth's surface can play an important role in controlling acid‐base processes in the oceans and thus climate, and suggest that these links should be more fully integrated into interpretive frameworks aimed at understanding Earth system evolution throughout Precambrian and Phanerozoic time.

Manganese-bearing minerals in ancient strata provide a particularly informative record of the redox potentials of ancient Earth surface environments due to the high specificity of species that can oxidize Mn(II). However, little is known about how this sedimentary archive might have been altered by processes occurring long after lithification, including the effects of metamorphism, fluid mobilization, and metasomatism. We investigated Mn mineralization across known metamorphic gradients in the Kaapvaal craton, South Africa, in Archean and early Paleoproterozoic age carbonate-, shale-, and iron formation-bearing marine strata. We sampled contemporaneous strata that record the drowning of the Campbellrand-Malmani carbonate platform and a transition to iron formation deposition in a range of localities, from two metamorphosed (greenschist and above, affected by the intrusion of the Bushveld igneous complex) and four better-preserved (sub-greenschist) deep subsurface drill cores. To evaluate the geochemistry and mineralization tied directly to petrographic textures and cross-cutting relationships, we combined bulk geochemistry with light and electron microscopy and synchrotron microprobe X-ray absorption spectroscopy and imaging to produce Mn speciation maps at the requisite micrometer length scales for these textures. Samples with lesser degrees of post-depositional transformation contained minor amounts of Mn(II) in early diagenetic marine carbonate cements and detrital carbonate grains, while metamorphosed samples typically contained Mn concentrated into a combination of coarse-grained and vein-filling carbonate phases (ankerite, siderite, and rhodochrosite), garnet and amphibole. Chemical imaging analyses of these more metamorphosed samples show that Mn is held by phases and textures that mineralized post-deposition and lithification, demonstrating that Mn was mobilized – at least locally – by metasomatic fluids, although it is difficult to distinguish whether this Mn was original to these strata or was introduced secondarily. Our results confirm that Mn can be mobilized and therefore caution should be applied when interpreting Mn enrichments in sedimentary rocks, especially when Mn enrichment is not geographically extensive and coincides with metamorphic processes.

Arctic river systems erode permafrost in their banks and mobilize particulate organic carbon (OC). Meandering rivers can entrain particulate OC from permafrost many meters below the depth of annual thaw, potentially enabling OC oxidation and the production of greenhouse gases. However, the amount and fate of permafrost OC that is mobilized by river erosion is uncertain. To constrain OC fluxes due to riverbank erosion and deposition, we collected riverbank and floodplain sediment samples along the Koyukuk River, which meanders through discontinuous permafrost in central Alaska. We measured sediment total OC (TOC), radiocarbon content, water content, bulk density, grain size, and floodplain stratigraphy. Radiocarbon abundance and TOC were higher in samples dominated by silt as compared to sand, which we used to map OC content onto floodplain stratigraphy and estimate carbon fluxes due to river meandering. Results showed that sediment being eroded from cutbanks and deposited as point bars had similar OC stocks (mean ± 1SD of 125.3 ± 13.1 kgOC m−2 in cutbanks versus 114.0 ± 15.7 kgOC m−2 in point bars) whether or not the banks contained permafrost. We also observed radiocarbon-depleted biospheric OC in both cutbanks and permafrost-free point bars. These results indicate that a significant fraction of aged biospheric OC that is liberated from floodplains by bank erosion is subsequently re-deposited in point bars, rather than being oxidized. The process of aging, erosion, and re-deposition of floodplain organic material may be intrinsic to river-floodplain dynamics, regardless of permafrost content.

Carbon dioxide (CO2) is the major carbonaceous component of many planetary atmospheres, which includes the Earth throughout its history. Carbon fixation chemistry—which reduces CO2 to organics, utilizing hydrogen as the stoichiometric reductant—usually requires high pressures and temperatures, and the yields of products of potential use to nascent biology are low. Here we demonstrate an efficient ultraviolet photoredox chemistry between CO2 and sulfite that generates organics and sulfate. The chemistry is initiated by electron photodetachment from sulfite to give sulfite radicals and hydrated electrons, which reduce CO2 to its radical anion. A network of reactions that generates citrate, malate, succinate and tartrate by irradiation of glycolate in the presence of sulfite was also revealed. The simplicity of this carboxysulfitic chemistry and the widespread occurrence and abundance of its feedstocks suggest that it could have readily taken place on the surfaces of rocky planets. The availability of the carboxylate products on early Earth could have driven the development of central carbon metabolism before the advent of biological CO2 fixation. Carbon dioxide is a substantial component of many planetary atmospheres, but reduction of carbon dioxide requires conditions and substrates that are rare on planetary surfaces. Now, the reduction of carbon dioxide to organic species with biological relevance has been photochemically coupled to the oxidation of sulfite, suggesting that prebiotic carbon fixation could take place on the surfaces of rocky planets.

Methods developed to explore the luminescent properties of the moon facilitated the development of techniques to infer terrestrial solar-induced chlorophyll fluorescence (SIF) from satellite instruments. While single SIF retrievals are inherently noisy, averaging many retrievals allows us to obtain highly accurate estimates. We analyzed several years of aggregated SIF data collected by the TROPOspheric Monitoring Instrument (TROPOMI) and the Orbiting Carbon Observatory-2 (OCO-2) over nonvegetated areas to explore the potential of SIF retrievals beyond the realm of photosynthesis. The fundamentally different retrievals at varying wavelengths in the near-infrared reveal that about 10% of all barren surfaces are weakly luminescent, while a few areas luminesce strongly—amounts comparable to SIF from vegetation. By means of lithological maps, we attributed the strongest luminescence signals to exposed carbonate sedimentary rocks. Besides a detailed evaluation of the signal properties, we discussed implications for SIF data sets and other remote sensing products.

Nitrogen is an essential element for life, with the availability of fixed nitrogen limiting productivity in many ecosystems. The return of oxidized nitrogen species to the atmospheric N2 pool is predominately catalyzed by microbial denitrification (NO3- → NO2- → NO → N2O → N2)1. Incomplete denitrification can produce N2O as a terminal product, leading to an increase in atmospheric N2O, a potent greenhouse and ozone-depleting gas2. The production of N2O is catalyzed by nitric oxide reductase (NOR) members of the heme-copper oxidoreductase (HCO) superfamily3. Here we use phylogenomics to identify a number of previously uncharacterized HCO families and propose that many of them (eNOR, sNOR, gNOR, and nNOR) perform nitric oxide reduction. These families have novel active-site structures and several have conserved proton channels, suggesting that they might be able to couple nitric oxide reduction to energy conservation. We isolated and biochemically characterized a member of the eNOR family from Rhodothermus marinus, verifying that it performs nitric oxide reduction both in vitro and in vivo. These newly identified NORs exhibit broad phylogenetic and environmental distributions, expanding the diversity of microbes that can perform denitrification. Phylogenetic analyses of the HCO superfamily demonstrate that nitric oxide reductases evolved multiple times independently from oxygen reductases, suggesting that complete denitrification evolved after aerobic respiration.

Permafrost soils store approximately twice the amount of carbon currently present in Earth’s atmosphere and are acutely impacted by climate change due to the polar amplification of increasing global temperature. Many organic-rich permafrost sediments are located on large river floodplains, where river channel migration periodically erodes and redeposits the upper tens of meters of sediment. Channel migration exerts a first-order control on the geographic distribution of permafrost and floodplain stratigraphy and thus may affect microbial habitats. To examine how river channel migration in discontinuous permafrost environments affects microbial community composition, we used amplicon sequencing of the 16S rRNA gene on sediment samples from floodplain cores and exposed riverbanks along the Koyukuk River, a large tributary of the Yukon River in west-central Alaska. Microbial communities are sensitive to permafrost thaw: communities found in deep samples thawed by the river closely resembled near-surface active-layer communities in nonmetric multidimensional scaling analyses but did not resemble floodplain permafrost communities at the same depth. Microbial communities also displayed lower diversity and evenness in permafrost than in both the active layer and permafrost-free point bars recently deposited by river channel migration. Taxonomic assignments based on 16S and quantitative PCR for the methyl coenzyme M reductase functional gene demonstrated that methanogens and methanotrophs are abundant in older permafrost-bearing deposits but not in younger, nonpermafrost point bar deposits. The results suggested that river migration, which regulates the distribution of permafrost, also modulates the distribution of microbes potentially capable of producing and consuming methane on the Koyukuk River floodplain. IMPORTANCE Arctic lowlands contain large quantities of soil organic carbon that is currently sequestered in permafrost. With rising temperatures, permafrost thaw may allow this carbon to be consumed by microbial communities and released to the atmosphere as carbon dioxide or methane. We used gene sequencing to determine the microbial communities present in the floodplain of a river running through discontinuous permafrost. We found that the river’s lateral movement across its floodplain influences the occurrence of certain microbial communities—in particular, methane-cycling microbes were present on the older, permafrost-bearing eroding riverbank but absent on the newly deposited river bars. Riverbank sediment had microbial communities more similar to those of the floodplain active-layer samples than permafrost samples from the same depth. Therefore, spatial patterns of river migration influence the distribution of microbial taxa relevant to the warming Arctic climate.

The deposition of marine carbonate rocks is influenced by climate and seawater chemistry. Carbonate platforms usually keep pace with subsidence and sea level rise but “platform drowning” occurs when carbonate sedimentation slows or when siliciclastics replace carbonates. Identifying specific mechanism(s) behind platform drowning is critical for understanding global environmental changes such as Ocean Anoxic Events (OAEs). We developed a model for OAEs which couples ocean basin redox processes to rates of carbonate sedimentation. Well-oxygenated oceans have steep gradients in saturation state such that deep-ocean dissolution is balanced by carbonate “overproduction” in shallow water. Through anaerobic metabolisms, deep-ocean anoxia reduces both dissolution and overproduction, leading to slower accumulation rates in shallow-water environments. This quasi-steady state response links carbonate sedimentation with longer timescales associated with redox changes. Redox-based drowning may have acted alongside other mechanisms to create spatially diverse patterns of platform drowning during Mesozoic OAEs and other Phanerozoic hyperthermal events.

Magnesium carbonates have been identified within the landing site of the Perseverance rover mission. This study reviews terrestrial analog environments and textural, mineral assemblage, isotopic, and elemental analyses that have been applied to establish formation conditions of magnesium carbonates. Magnesium carbonates form in five distinct settings: ultramafic rock-hosted veins, the matrix of carbonated peridotite, nodules in soil, alkaline lake, and playa deposits, and as diagenetic replacements within lime—and dolostones. Dominant textures include fine-grained or microcrystalline veins, nodules, and crusts. Microbial influences on formation are recorded in thrombolites, stromatolites, crinkly, and pustular laminites, spheroids, and filamentous microstructures. Mineral assemblages, fluid inclusions, and carbon, oxygen, magnesium, and clumped isotopes of carbon and oxygen have been used to determine the sources of carbon, magnesium, and fluid for magnesium carbonates as well as their temperatures of formation. Isotopic signatures in ultramafic rock-hosted magnesium carbonates reveal that they form by either low-temperature meteoric water infiltration and alteration, hydrothermal alteration, or metamorphic processes. Isotopic compositions of lacustrine magnesium carbonate record precipitation from lake water, evaporation processes, and ambient formation temperatures. Assessment of these features with similar analytical techniques applied to returned Martian samples can establish whether carbonates on ancient Mars were formed at high or low temperature conditions in the surface or subsurface through abiotic or biotic processes. The timing of carbonate formation processes could be constrained by 147Sm-143Nd isochron, U-Pb concordia, 207Pb-206Pb isochron radiometric dating as well as 3He, 21Ne, 22Ne, or 36Ar surface exposure dating of returned Martian magnesium carbonate samples., Plain Language Summary Magnesium carbonate minerals rarely form large deposits on Earth and because they constitute such a small proportion of the terrestrial carbonate record in comparison to calcium-rich carbonates, they have received little attention. In contrast, the largest carbonate deposit detected on Mars has magnesium carbonate, and it has been detected at the landing site of the 2020 mission where the Perseverance rover will collect samples for return to Earth. We synthesized the field observations and laboratory experiments that pertain to magnesium carbonates formed on Earth and find that they form in five types of environments as follows: within veins or in the bulk volume of magnesium-rich rocks, soils, alkaline or salty lakes, and as replacements of previously formed calcium-rich carbonate minerals. Conceptually, these environments may be analogs for ancient Martian magnesium carbonate-forming environments. Magnesium carbonates formed in some environments are capable of preserving remnants of microbes, especially if magnesium carbonates formed characteristic large-scale clotted or vertical column shapes or microscale spherical and laminated textures. If life had ever originated on Mars, these would be key materials to investigate for biosignatures. Finally, a number of analytical techniques are discussed that can be performed on magnesium carbonate rocks collected by Perseverance when returned to Earth.

Mono Lake is a closed‐basin, hypersaline, alkaline lake located in Eastern Sierra Nevada, California, that is dominated by microbial life. This unique ecosystem offers a natural laboratory for probing microbial community responses to environmental change. In 2017, a heavy snowpack and subsequent runoff led Mono Lake to transition from annually mixed (monomictic) to indefinitely stratified (meromictic). We followed microbial succession during this limnological shift, establishing a two‐year (2017–2018) water‐column time series of geochemical and microbiological data. Following meromictic conditions, anoxia persisted below the chemocline and reduced compounds such as sulfide and ammonium increased in concentration from near 0 to ~400 and ~150 µM, respectively, throughout 2018. We observed significant microbial succession, with trends varying by water depth. In the epilimnion (above the chemocline), aerobic heterotrophs were displaced by phototrophic genera when a large bloom of cyanobacteria appeared in fall 2018. Bacteria in the hypolimnion (below the chemocline) had a delayed, but systematic, response reflecting colonization by sediment “seed bank” communities. Phototrophic sulfide‐oxidizing bacteria appeared first in summer 2017, followed by microbes associated with anaerobic fermentation in spring 2018, and eventually sulfate‐reducing taxa by fall 2018. This slow shift indicated that multi‐year meromixis was required to establish a sulfate‐reducing community in Mono Lake, although sulfide oxidizers thrive throughout mixing regimes. The abundant green alga Picocystis remained the dominant primary producer during the meromixis event, abundant throughout the water column including in the hypolimnion despite the absence of light and prevalence of sulfide. Our study adds to the growing literature describing microbial resistance and resilience during lake mixing events related to climatic events and environmental change.