Determining the Aerosols of Earth's Archean PaleoAtmosphere

Follow the Carbon: Isotopic Labeling Studies of Early Earth Aerosol

Authors:

Hicks et al

Abstract:

Despite the faint young Sun, early Earth might have been kept warm by an atmosphere containing the greenhouse gases CH4 and CO2 in mixing ratios higher than those found on Earth today. Laboratory and modeling studies suggest that an atmosphere containing these trace gases could lead to the formation of organic aerosol haze due to UV photochemistry. Chemical mechanisms proposed to explain haze formation rely on CH4 as the source of carbon and treat CO2 as a source of oxygen only, but this has not previously been verified experimentally. In the present work, we use isotopically labeled precursor gases and unit-mass resolution (UMR) and high-resolution (HR) aerosol mass spectrometry to examine the sources of carbon and oxygen to photochemical aerosol formed in a CH4/CO2/N2 atmosphere. UMR results suggest that CH4 contributes 70–100% of carbon in the aerosol, while HR results constrain the value from 94% to 100%. We also confirm that CO2 contributes approximately 10% of the total mass to the aerosol as oxygen. These results have implications for the geochemical interpretations of inclusions found in Archean rocks on Earth and for the astrobiological potential of other planetary atmospheres.

Romer's Gap Plugged: 5 new Tetrapods From Tournaisian Mississippian Carboniferous Scotland

Phylogenetic and environmental context of a Tournaisian tetrapod fauna

Authors:

Clack et al

Abstract:

The end-Devonian to mid-Mississippian time interval has long been known for its depauperate palaeontological record, especially for tetrapods. This interval encapsulates the time of increasing terrestriality among tetrapods, but only two Tournaisian localities previously produced tetrapod fossils. Here we describe five new Tournaisian tetrapods (Perittodus apsconditus, Koilops herma, Ossirarus kierani, Diploradus austiumensis and Aytonerpeton microps) from two localities in their environmental context. A phylogenetic analysis retrieved three taxa as stem tetrapods, interspersed among Devonian and Carboniferous forms, and two as stem amphibians, suggesting a deep split among crown tetrapods. We also illustrate new tetrapod specimens from these and additional localities in the Scottish Borders region. The new taxa and specimens suggest that tetrapod diversification was well established by the Tournaisian. Sedimentary evidence indicates that the tetrapod fossils are usually associated with sandy siltstones overlying wetland palaeosols. Tetrapods were probably living on vegetated surfaces that were subsequently flooded. We show that atmospheric oxygen levels were stable across the Devonian/Carboniferous boundary, and did not inhibit the evolution of terrestriality. This wealth of tetrapods from Tournaisian localities highlights the potential for discoveries elsewhere.

pop sci write up.

No Apparent Spike of Carbon dioxide Across Cretaceous-Paleogene Boundary

Global trends of pCO2 across the Cretaceous–Paleogene boundary supported by the first Southern Hemisphere stomatal proxy-based pCO2 reconstruction

Authors:

Steinthorsdottir et al

Abstract:

Reliable reconstructions of atmospheric carbon dioxide concentrations (pCO2) are required at higher resolution than currently available to help resolve the relationship between mass extinctions and changes in palaeo-pCO2 levels. Such reconstructions are needed: 1, at a high temporal resolution for constraining the pre- and post-extinction atmospheres; and 2, at a sufficient spatial resolution to constrain potential inter-hemispheric differences. Here we estimate pCO2 based on fossil Lauraceae leaf cuticle specimens derived from three localities with strata spanning the latest Cretaceous to the mid-Paleocene, including a new Cretaceous–Paleogene boundary (K–Pg) locality, in New Zealand. We use two independent methods of stomatal density-based pCO2 reconstructions; a transfer function calibrated using herbarium material and the stomatal ratio method, producing three calibration sets. Our results based on the mean values of each of the three calibration methods indicate pCO2 ranging between ca. 460 and 650 ppm during the latest Cretaceous, falling precipitously to average values between ca. 360 and 430 ppm across the K–Pg boundary, and further to ca. 305–320 ppm in the mid-Paleocene. A ‘spike’ of extremely high pCO2 at the K–Pg could not be confirmed, but our results are, nonetheless, consistent with previously published pCO2 records from the Northern Hemisphere, and show that stomatal density worldwide was responding to significant changes in pCO2 across the K–Pg.

Oxygen Levels may Have Never Crashed During the Mesozoic

A modeling case for high atmospheric oxygen concentrations during the Mesozoic and Cenozoic

Authors:

Mills et al

Abstract:

Changes in atmospheric oxygen concentration over Earth history are commonly related to the evolution of animals and plants. But there is no direct geochemical proxy for O2 levels, meaning that estimations rely heavily on modeling approaches. The results of such studies differ greatly, to the extent that today's atmospheric mixing ratio of 21% might be either the highest or lowest level during the past 200 m.y. Long-term oxygen sources, such as the burial in sediments of reduced carbon and sulfur species, are calculated in models by representation of nutrient cycling and estimation of productivity, or by isotope mass balance (IMB)—a technique in which burial rates are inferred in order to match known isotope records. Studies utilizing these different techniques produce conflicting estimates for paleoatmospheric O2, with nutrient-weathering models estimating concentrations close to, or above, that of the present day, and IMB models estimating low O2, especially during the Mesozoic. Here we re-assess the IMB technique using the COPSE biogeochemical model. IMB modelling is confirmed to be highly sensitive to assumed carbonate δ13C, and when this input is defined following recent compilations, predicted O2 is significantly higher and in reasonable agreement with that of non-IMB techniques. We conclude that there is no model-based support for low atmospheric oxygen concentrations during the past 200 m.y. High Mesozoic O2 is consistent with wildfire records and the development of plant fire adaptions, but links between O2 and mammal evolution appear more tenuous.

The Strontium Cycle of the NeoProterozoic was Driven by Seemingly Unique Paleogeography

Paleogeographic forcing of the strontium isotopic cycle in the Neoproterozoic

Authors:

Goddéris et al

Abstract:

The period spanning from 825 to 540 Ma is characterized by major changes in the surficial Earth system. This extraordinary interval starts with the breakup of the Rodinia supercontinent and eruption of a series of large igneous provinces and ends with the assembly of Gondwana, giving rise to the Pan-African orogenies. This paleogeographic reorganization is accompanied by a global climatic cooling, including the paroxysmal Cryogenian “snowball” glacial events. The 87Sr/86Sr of seawater displays a major long-term rise over this interval that is punctuated by episodic, smaller declines and inflections. We use a coupled deep time climate-carbon numerical model to explore the complex role of tectonics and climate on this distinct evolution in seawater 87Sr/86Sr. We show that the modulation of the weathering of the erupted large igneous provinces by continental drift explains the changes in seawater 87Sr/86Sr from 800 to 635 Ma. The subsequent sharp rise in seawater 87Sr/86Sr from 635 to 580 Ma is the result of erosion of radiogenic crust exposed in the Pan-African orogens. Coeval evolution of atmospheric CO2 displays a decrease from about 80 times the pre-industrial level around 800 Ma to 5 times just before the beginning of the Phanerozoic.

Methanotrophic Microbes in the Archean Oceans

Lacustrine facies dependence of highly 13C-depleted organic matter during the global age of methanotrophy

Authors:

Flannery et al

Abstract:

Highly 13C-depleted organic matter reported from Neoarchean formations worldwide has led to the concept of a “Global Age of Methanotrophy” (GAM) in the Neoarchean. A temporal peak in the GAM is suggested by values as low as −61‰ that are reported from rocks deposited at ∼2.7 Ga. Here we analyse previously reported values, report new field observations and isotope data, and re-evaluate the depositional settings of several units of this age. We find a statistically significant lowering of δ13Corg values in units of Neoarchean age compared to values reported from other Precambrian intervals, both older and younger, confirming the existence of the GAM. However, we also report a correlation between very low δ13Corg values and lacustrine units deposited during the Neoarchean. We hypothesize methanogenesis may have been promoted in some Neoarchean lakes due to local deficiencies of oxidants, specifically Fe3+ and SO4, relative to the Archean oceans. Lower availability of these oxidants could have limited higher energy yield metabolisms such as sulfate and iron reduction and provided an ecological niche for methanogens, ultimately resulting in the local burial of biomass highly depleted in 13C. We conclude that the exceptionally low δ13Corg values reported from formations deposited at ∼2.7 Ga could represent the prevalence of closed basin depositional environments preserved in the limited outcrop available, rather than a peak in the global age of methanotrophy at this time.

Evidence of Atmospheric Sulfur During the MesoArchean

An atmospheric source of S in Mesoarchaean structurally-controlled gold mineralisation of the Barberton Greenstone Belt

Authors:

Agangi et al

Abstract:

The Barberton Greenstone Belt of southern Africa hosts several Mesoarchaean gold deposits. The ores were mostly formed in greenschist facies conditions, and occur as hydrothermal alteration zones around extensional faults that truncate and post-date the main compressional structures of the greenstone belt. Ore deposition was accompanied by the intrusion of porphyries, which has led to the hypothesis that gold may have been sourced from magmas. Because the transport of Au in the hydrothermal fluids is widely believed to have involved S complexes, tracing the origin of S may place strong constraints on the origin of Au. We measured multiple S isotopes in sulfide ore from Sheba and Fairview mines of the Barberton Greenstone Belt to distinguish “deep” S sources (e.g. magmas) from “surface” S sources (i.e. rocks of the volcano-sedimentary succession that contain S processed in the atmosphere preserved as sulfide and sulfate minerals). Ion probe (SIMS) analyses of pyrite from ore zones indicate mass-independent fractionation of S isotopes (Δ33S = −0.6‰ to +1.0‰) and the distribution of the analyses in the Δ33S–δ34S space matches the distribution peak of previously published analyses of pyrite from the entire volcano-sedimentary succession. Notwithstanding that the H2O–CO2 components of the fluids may have been introduced from a deep source external to the greenstone belt rocks, the fact that S bears an atmospheric signature suggests the hypothesis that the source of Au should also be identified in the supracrustal succession of the greenstone belt. Our findings differ from conclusions of previous studies of other Archaean shear-hosted Au deposits based on mineralogical and isotopic evidence, which suggested a magmatic or mantle source for Au, and imply that there is no single model that can be applied to this type of mineralisation in the Archaean.

Methane Did NOT Warm the Early Earth

For at least a billion years of the distant past, planet Earth should have been frozen over but wasn't. Scientists thought they knew why, but a new modeling study from the Alternative Earths team of the NASA Astrobiology Institute has fired the lead actor in that long-accepted scenario.

Humans worry about greenhouse gases, but between 1.8 billion and 800 million years ago, microscopic ocean dwellers really needed them. The sun was 10 to 15 percent dimmer than it is today--too weak to warm the planet on its own. Earth required a potent mix of heat-trapping gases to keep the oceans liquid and livable.

For decades, atmospheric scientists cast methane in the leading role. The thinking was that methane, with 34 times the heat-trapping capacity of carbon dioxide, could have reigned supreme for most of the first 3.5 billion years of Earth history, when oxygen was absent initially and little more than a whiff later on. (Nowadays oxygen is one-fifth of the air we breathe, and it destroys methane in a matter of years.)

"A proper accounting of biogeochemical cycles in the oceans reveals that methane has a much more powerful foe than oxygen," said Stephanie Olson, a graduate student at the University of California, Riverside, a member of the Alternative Earths team and lead author of the new study published September 26 in the Proceedings of the National Academy of Sciences. "You can't get significant methane out of the ocean once there is sulfate."

Sulfate wasn't a factor until oxygen appeared in the atmosphere and triggered oxidative weathering of rocks on land. The breakdown of minerals such as pyrite produces sulfate, which then flows down rivers to the oceans. Less oxygen means less sulfate, but even 1 percent of the modern abundance is sufficient to kill methane, Olson said.

link.

Evidence of Fluctuating Paleoatmospheric Oxygen Levels Before and After the Cryogenian Marinoan (Snowball Earth) Glaciations

Chromium isotope, REE and redox-sensitive trace element chemostratigraphy across the late Neoproterozoic Ghaub glaciation, Otavi Group, Namibia

Authors:

Rodler et al

Abstract:

Chromium isotopes constitute a powerful paleoenvironmental tracer recording fluctuations of atmospheric oxygenation and continental weathering thus facilitating the reconstruction of the redox state of ancient seawater. We use the δ53Cr signature coupled with REE+Y patterns and redox-sensitive trace elements to monitor environmental changes recorded by marine carbonates of the Otavi Group, Namibia. These carbonates were deposited in a platform and foreslope setting in subtropical latitudes during the Neoproterozoic and comprise the transition from a marine depositional setting through glaciation into a postglacial environment in four stages. Preglacial carbonates (Stage 1) yield positively fractionated δ53Cr values, increased U and Mn concentrations, indicative of mobilization during oxidative terrestrial weathering and stabilization in oxic surface waters. Carbonates deposited just before the Ghaub diamictites (Stage 2) record δ53Cr values (>+0.4 ‰) comparable to modern seawater and negative Ce anomalies (∼0.7) characteristic for oxygenated seawater. We interpret this as a pulse of intense oxidative weathering shortly before the advance of the glaciers. Marginal shale contamination persists in carbonates of both sections and is slightly elevated during the glacial aftermath; Cr is vulnerable towards detrital contamination. Early postglacial cap dolostones (Stage 3) were influenced by enhanced detrital contamination potentially supplied by freshwater particulate load, which was then drastically reduced in the overlying postglacial limestones in the upper Maieberg Fm (Stage 4) where near-preglacial δ53Cr values are reached again. REE+Y patterns along with Eu and Ce anomalies record a transformation from a marine, slightly anoxic and stratified water column with distal hydrothermal influence to a freshwater-influenced depositional environment with decreased hydrothermal activity and fluctuating oxic surface water conditions after glacial retreat. Here, we demonstrate that carbonate δ53Cr signatures are sensitive to changes in continental weathering balanced between detrital contamination and oxidative weathering on land and are capable of tracing fluctuating redox conditions prior and after one of the major syn-Marinoan glaciations.

Atmospheric Oxygen Dropped .7% Last 800,000 Years, .1% in Last 100 Years

Princeton University researchers have compiled 30 years of data to construct the first ice core-based record of atmospheric oxygen concentrations spanning the past 800,000 years, according to a paper in the journal Science.

The record shows that atmospheric oxygen has declined 0.7 percent relative to current atmospheric-oxygen concentrations, a reasonable pace by geological standards, the researchers said. During the past 100 years, however, atmospheric oxygen has declined by a comparatively speedy 0.1 percent because of the burning of fossil fuels, which consumes oxygen and produces carbon dioxide.

Curiously, the decline in atmospheric oxygen over the past 800,000 years was not accompanied by any significant increase in the average amount of carbon dioxide in the atmosphere, though carbon dioxide concentrations do vary over individual ice age cycles. To explain this apparent paradox, the researchers called upon a theory for how the global carbon cycle, atmospheric carbon dioxide and Earth's temperature are linked on geologic timescales.

"The planet has various processes that can keep carbon dioxide levels in check," said first author Daniel Stolper, a postdoctoral research associate in Princeton's Department of Geosciences. The researchers discuss a process known as "silicate weathering" in particular, wherein carbon dioxide reacts with exposed rock to produce, eventually, calcium carbonate minerals, which trap carbon dioxide in a solid form. As temperatures rise due to higher carbon dioxide in the atmosphere, silicate-weathering rates are hypothesized to increase and remove carbon dioxide from the atmosphere faster.

Stolper and his co-authors suggest that the extra carbon dioxide emitted due to declining oxygen concentrations in the atmosphere stimulated silicate weathering, which stabilized carbon dioxide but allowed oxygen to continue to decline.

"The oxygen record is telling us there's also a change in the amount of carbon dioxide [that was created when oxygen was removed] entering the atmosphere and ocean," said co-author John Higgins, Princeton assistant professor of geosciences. "However, atmospheric carbon dioxide levels aren't changing because the Earth has had time to respond via increased silicate-weathering rates.

link.

Earliest land plants created modern levels of atmospheric oxygen

Earliest land plants created modern levels of atmospheric oxygen

Authors:

Lenton et al

Abstract:

The progressive oxygenation of the Earth’s atmosphere was pivotal to the evolution of life, but the puzzle of when and how atmospheric oxygen (O2) first approached modern levels (∼21%) remains unresolved. Redox proxy data indicate the deep oceans were oxygenated during 435–392 Ma, and the appearance of fossil charcoal indicates O2 >15–17% by 420–400 Ma. However, existing models have failed to predict oxygenation at this time. Here we show that the earliest plants, which colonized the land surface from ∼470 Ma onward, were responsible for this mid-Paleozoic oxygenation event, through greatly increasing global organic carbon burial—the net long-term source of O2. We use a trait-based ecophysiological model to predict that cryptogamic vegetation cover could have achieved ∼30% of today’s global terrestrial net primary productivity by ∼445 Ma. Data from modern bryophytes suggests this plentiful early plant material had a much higher molar C:P ratio (∼2,000) than marine biomass (∼100), such that a given weathering flux of phosphorus could support more organic carbon burial. Furthermore, recent experiments suggest that early plants selectively increased the flux of phosphorus (relative to alkalinity) weathered from rocks. Combining these effects in a model of long-term biogeochemical cycling, we reproduce a sustained +2‰ increase in the carbonate carbon isotope (δ13C) record by ∼445 Ma, and predict a corresponding rise in O2 to present levels by 420–400 Ma, consistent with geochemical data. This oxygen rise represents a permanent shift in regulatory regime to one where fire-mediated negative feedbacks stabilize high O2 levels.

pop sci write up.

'Whiffs' of Oxygen From Archean Sediments

Evidence for a reducing Archean ambient mantle and its effects on the carbon cycle

Authors:

Aulbach et al

Abstract:

Chemical reduction-oxidation mechanisms within mantle rocks link to the terrestrial carbon cycle by influencing the depth at which magmas can form, their composition, and ultimately the chemistry of gases released into the atmosphere. The oxidation state of the uppermost mantle has been widely accepted to be unchanged over the past 3800 m.y., based on the abundance of redox-sensitive elements in greenstone belt–associated samples of different ages. However, the redox signal in those rocks may have been obscured by their complex origins and emplacement on continental margins. In contrast, the source and processes occurring during decompression melting at spreading ridges are relatively well constrained. We retrieve primary redox conditions from metamorphosed mid-oceanic ridge basalts (MORBs) and picrites of various ages (ca. 3000–550 Ma), using V/Sc as a broad redox proxy. Average V/Sc values for Proterozoic suites (7.0 ± 1.4, 2σ, n = 6) are similar to those of modern MORB (6.8 ± 1.6), whereas Archean suites have lower V/Sc (5.2 ± 0.4, n = 5). The lower Archean V/Sc is interpreted to reflect both deeper melt extraction from the uppermost mantle, which becomes more reduced with depth, and an intrinsically lower redox state. The pressure-corrected oxygen fugacity (expressed relative to the fayalite-magnetite-quartz buffer, ΔFMQ, at 1 GPa) of Archean sample suites (ΔFMQ –1.19 ± 0.33, 2σ) is significantly lower than that of post-Archean sample suites, including MORB (ΔFMQ –0.26 ± 0.44). Our results imply that the reducing Archean atmosphere was in equilibrium with Earth's mantle, and further suggest that magmatic gases crossed the threshold that allowed a build-up in atmospheric O2 levels ca. 3000 Ma, accompanied by the first "whiffs" of oxygen in sediments of that age.

Evidence of Wild Fires From Cisuralian Permian China

First report of Cisuralian (early Permian) charcoal layers within a coal bed from Baode, North China with reference to global wildfire distribution

Authors:

Yan et al

Abstract:

Fossil charcoal is reported for the first time from a Cisuralian coal bed of the Shanxi Formation in the Qiaotou Section, Baode, Shanxi, North China. Based on anatomical characteristics, these charcoal fragments consist of coniferous or cordaitalean xylem, unidentified primary xylem and cordaitalean and possible fern leaves. These charcoal fragments represent the evidence of palaeowildfire taking place in tropical peat swamps during the Cisuralian in Cathaysia. The palaeowildfire is most likely to be a surface fire and burning litter and shrubby vegetation. Fire frequency for this early Permian peat swamp might have been on the order of 176–(294–588)–1429 years, close to modern values. Compared with modern analogues, the North China Block during the Cisuralian was probably wet in general but could be occasionally seasonally dry for short time intervals. Previous charcoal and inertinite records moreover indicate that palaeowildfires were globally common during the Cisuralian. Overall, more wildfire evidence was found in the Artinskian–Kungurian than the Asselian-Sakmarian (except in the Euramerican Realm), probably due to more suitable regional climate, vegetation to fuel fires and taphonomic circumstances.

Earth’s oxygen cycle and the evolution of animal life

Earth’s oxygen cycle and the evolution of animal life

Authors:

Reinhard et al

Abstract:

The emergence and expansion of complex eukaryotic life on Earth is linked at a basic level to the secular evolution of surface oxygen levels. However, the role that planetary redox evolution has played in controlling the timing of metazoan (animal) emergence and diversification, if any, has been intensely debated. Discussion has gravitated toward threshold levels of environmental free oxygen (O2) necessary for early evolving animals to survive under controlled conditions. However, defining such thresholds in practice is not straightforward, and environmental O2 levels can potentially constrain animal life in ways distinct from threshold O2 tolerance. Herein, we quantitatively explore one aspect of the evolutionary coupling between animal life and Earth’s oxygen cycle—the influence of spatial and temporal variability in surface ocean O2 levels on the ecology of early metazoan organisms. Through the application of a series of quantitative biogeochemical models, we find that large spatiotemporal variations in surface ocean O2 levels and pervasive benthic anoxia are expected in a world with much lower atmospheric pO2 than at present, resulting in severe ecological constraints and a challenging evolutionary landscape for early metazoan life. We argue that these effects, when considered in the light of synergistic interactions with other environmental parameters and variable O2 demand throughout an organism’s life history, would have resulted in long-term evolutionary and ecological inhibition of animal life on Earth for much of Middle Proterozoic time (∼1.8–0.8 billion years ago).

A new way of Determining Paleoatmospheric Oxygen Content

Paradigm shift in determining Neoproterozoic atmospheric oxygen

Authors:

Blamey et al

Abstract:

We present a new and innovative way of determining the oxygen level of Earth's past atmosphere by directly measuring inclusion gases trapped in halite. After intensive screening using multiple depositional, textural/fabric, and geochemical parameters, we determined that tectonically undisturbed cumulate, chevron, and cornet halite inclusions may retain atmospheric gas during crystallization from shallow saline, lagoonal, and/or saltpan brine. These are the first measurements of inclusion gas for the Neoproterozoic obtained from 815 ± 15–m.y.–old Browne Formation chevron halite of the Officer Basin, southwest Australia. The 31 gas measurements afford us a direct glimpse of the composition of the mid- to late Neoproterozoic atmosphere and register an average oxygen content of 10.9%. The measured pO2 puts oxygenation of Earth's paleoatmosphere ∼100–200 m.y. ahead of current models and proxy studies. It also puts oxygenation of the Neoproterozoic atmosphere in agreement with time of diversification of eukaryotes and in advance of the emergence of marine animal life.

Anomalies in Archean Sulfate Signatures

Multiple sulfur-isotope signatures in Archean sulfates and their implications for the chemistry and dynamics of the early atmosphere

Authors:

Muller et al

Abstract:

Sulfur isotopic anomalies (∆33S and ∆36S) have been used to trace the redox evolution of the Precambrian atmosphere and to document the photochemistry and transport properties of the modern atmosphere. Recently, it was shown that modern sulfate aerosols formed in an oxidizing atmosphere can display important isotopic anomalies, thus questioning the significance of Archean sulfate deposits. Here, we performed in situ 4S-isotope measurements of 3.2- and 3.5-billion-year (Ga)-old sulfates. This in situ approach allows us to investigate the diversity of Archean sulfate texture and mineralogy with unprecedented resolution and from then on to deconvolute the ocean and atmosphere Archean sulfur cycle. A striking feature of our data is a bimodal distribution of δ34S values at ∼+5‰ and +9‰, which is matched by modern sulfate aerosols. The peak at +5‰ represents barite of different ages and host-rock lithology showing a wide range of ∆33S between −1.77‰ and +0.24‰. These barites are interpreted as primary volcanic emissions formed by SO2 photochemical processes with variable contribution of carbonyl sulfide (OCS) shielding in an evolving volcanic plume. The δ34S peak at +9‰ is associated with non–33S-anomalous barites displaying negative ∆36S values, which are best interpreted as volcanic sulfate aerosols formed from OCS photolysis. Our findings confirm the occurrence of a volcanic photochemical pathway specific to the early reduced atmosphere but identify variability within the Archean sulfate isotope record that suggests persistence throughout Earth history of photochemical reactions characteristic of the present-day stratosphere.

Hints of a Higher Than Expected Oxidation From During MesoArchean

Uranium irradiation history of carbonado diamond; implications for Paleoarchean oxidation in the São Francisco craton

Authors:

Magee et al

Abstract:

Carbonado is a porous polycrystalline diamond rock found in central African and Brazilian placer deposits. It contains unsupported radiogenic isotopes of He, Ne, Kr, Xe, and Pb. Here we show that these, and the radiation-related defects introduced to the diamond structure, are a result of uranium precipitation, with no isotopic or spectroscopic evidence of Th enrichment. The daughter products are unsupported due to Proterozoic U remobilization. Combining existing carbonado Pb isotope data with recent studies of the geochronology of the tectonic evolution of the São Francisco craton (eastern South America) reveals that the most likely scenario is Paleoarchean uranium enrichment of carbonado, followed by Mesoproterozoic uranium dissolution. Under all possible scenarios, the carbonado radiation damage history requires U mobilization in the Mesoarchean or late Paleoarchean. This is consistent with recent studies of South Africa and India Mesoarchean paleosols, which also show evidence for local oxygen activity greater than that of the Archean atmosphere and ocean. While those studies rely on whole-rock trace element and transition metal stable isotope measurements, this combination of crystallographic defects, sedimentary geochronology, and radiogenic isotopes supports the same conclusions of nonmarine, near-surface Archean oxygen enhancement.

Reworking of atmospheric sulfur in a Paleoarchean hydrothermal system

Reworking of atmospheric sulfur in a Paleoarchean hydrothermal system at Londozi, Barberton Greenstone Belt, Swaziland

Authors:

Roerdink et al

Abstract:

Anomalous fractionation of the minor isotopes of sulfur (Δ33S, Δ36S) in Archean pyrite is thought to reflect photochemical reactions in an anoxic atmosphere, with most samples falling along a reference array with Δ36S/Δ33S ≈ −1. Small deviations from this array record microbial sulfate reduction or changes in atmospheric source reactions. Here, we argue that reworking of atmospheric sulfur with distinct minor sulfur isotope ratios (Δ36S/Δ33S ≠ −1) produced additional variability in sulfide Δ33S and Δ36S-values in a 3.52 Ga hydrothermal barite deposit at Londozi, Barberton Greenstone Belt, Swaziland. In situ measurement of the four stable sulfur isotopes in pyrite revealed Δ36S–Δ33S relationships and a Δ36S/Δ33S trend (−3.2 ± 0.4), which is significantly different from the co-variation between Δ36S and Δ33S in the co-existing barite that reflects ambient Paleoarchean seawater sulfate. This argues against biological or thermochemical sulfate reduction at the time of barite deposition, and requires incorporation of sulfide generated in a chemically distinct atmosphere before 3.52 Ga. We propose a model that combines reworking of this sulfur by hydrothermal leaching, deep mixing with juvenile sulfur and surface mixing with biogenic sulfide to explain the observed variation in δ34S, Δ33S and Δ36S. These interactions between abiotic and biological processes in the Londozi hydrothermal system complicate the interpretation of biosignatures based on deviations in Δ33S and Δ36S from the Archean reference array.

Evidence for Atmospheric Oxygenation During Ectasian MesoProterozoic?!

Pyrite trace element chemistry of the Velkerri Formation, Roper Group, McArthur Basin: Evidence for atmospheric oxygenation during the Boring Billion

Authors:

Mukherjee et al

Abstract:

The trace element content of sedimentary pyrite in black shales of varying ages has recently been used to construct secular trends of trace element variation in the ocean. The approach also has potential to be used as a proxy for estimating evolution of the redox state of the ocean/atmosphere system through time. Here, we apply a combination of whole-rock chemostratigraphy and laser ablation-inductively coupled plasma-mass spectrometer (LA-ICP-MS) analyses of marine pyrite to the carbonaceous mudstones of the Mesoproterozoic (∼1400 Ma) Velkerri Formation, and underlying Corcoran Formation, Roper Group, McArthur Basin to interpret and compare basin water conditions and basinal trace element chemistry at the time of sedimentation.

Our results suggest that the black shales of the Velkerri Formation deposited under different geochemical conditions in comparison to the underlying Corcoran Formation. This proportionate difference is manifested in the form of high total organic carbon (TOC) contents coupled with an increase of trace elements such as P, Mo, Cd, Se, Ni, Se/Co, Ni/Co in the mudstones of Upper Velkerri Formation in comparison to Lower Velkerri and underlying Corcoran Formation. Cobalt on the other hand, exhibits an opposite trend compared to other redox sensitive trace elements (Mo, Se) due to its unique redox chemistry, particularly the cationic nature of its soluble species making Se/Co a useful proxy for redox conditions of the atmosphere. This progressive increment in trace elements (P, Mo, Cd, Se, Ni, Se/Co, Ni/Co) up stratigraphy from Corcoran Formation to Lower Velkerri Formation to Upper Velkerri is herein attributed to an increase in nutrient trace element supply into the marine reservoir, possibly in response to tectonic activity and an increase in oxygen in the atmosphere. This increased nutrient supply subsequently promoted an increase in primary productivity as indicated by high TOC contents in the Upper Velkerri Formation. This positive change in nutrient supply also coincides with an increased supply of sulphate to the ocean (modelled paleo-seawater [SO42−]) as evidenced by previous sulphur isotope studies and development of morphological complexity in eukaryotes based on paleontological observations of previous workers. The totality of evidence from this study and previous studies, suggest that there was a possible oxygenation event around ∼1400 Ma. This is in contrast with the general notion that Mesoproterozoic oxygen levels were low and devoid of significant fluctuations.

A Record of low Atmospheric Oxygen From the Proterozoic

A shale-hosted Cr isotope record of low atmospheric oxygen during the Proterozoic

Authors:

Cole et al

Abstract:

The emergence and expansion of animal life on Earth represents a dramatic shift in the structure and complexity of the biosphere. A lack of firm constraints on surface oxygen levels during the mid-Proterozoic has resulted in heated debate as to whether the rise and earliest diversification of animals was directly linked to a change in environmental oxygen levels or, instead, simply reflects the timing of innovations in gene expression and developmental regulation and was independent of a direct environmental trigger. Here, we present chromium (Cr) isotope data from marine black shales that provide evidence for minimal Cr oxidation throughout the mid-Proterozoic leading up to the diversification of eukaryotes and the rise of animals during the late Neoproterozoic. This observation requires very low background oxygen levels (less than 1% of present atmospheric levels). Accepting previously proposed estimates of pO2 levels needed to induce Cr isotope fractionation, our data provide support for the persistence of an Earth system in which baseline atmospheric pO2 would have been low enough to inhibit the diversification of animals until ca. 800 Ma. More generally, evidence for a delayed rise of atmospheric oxygen strongly suggests that environmental factors have played a fundamental role in controlling the emergence and expansion of complex life on Earth.